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Transient [3,3] Cope rearrangement of 3,3-dicyano-1,5-dienes: computational analysis and 2-step synthesis of arylcycloheptanes.
A simple and modular route to arylcycloheptene scaffolds is reported. The two-step route from Knoevenagel adducts and allylic electrophiles is made possible through the design of a Cope rearrangement that utilizes a "traceless" activating group to promote an otherwise thermodynamically unfavorable transformation. Experimentally, the [3,3] rearrangement occurrs transiently at room temperature with a computed barrier of 19.5 kcal mol-1, which ultimately allows for three-component bis-allylation. Ring-closing metathesis delivers the arylcycloheptane and removes the activating group. This report describes the design and optimization of the methodology, scope and mechanistic studies, and computational analysis
Antidepressant drugs and the response in the placebo group: the real problem lies in our understanding of the issue
In a recent paper, Horder and colleagues (Horder et al., 2010, J Psychopharmacol 25: 1277–1288) have suggested that the mainproblem in the Kirsch analysis is methodological. We argue that the results are similar irrespective of the method used. In our opinion the data suggest that placebo and drug effects are non-additive: antidepressants act independently of depression severity, while the placebo effect is present only in milder cases. While the response in the placebo group is due to unstable ‘noise’ and ‘artefacts’, the medication effect is reliable, valid and stable
The QCD sign problem and dynamical simulations of random matrices
At nonzero quark chemical potential dynamical lattice simulations of QCD are
hindered by the sign problem caused by the complex fermion determinant. The
severity of the sign problem can be assessed by the average phase of the
fermion determinant. In an earlier paper we derived a formula for the
microscopic limit of the average phase for general topology using chiral random
matrix theory. In the current paper we present an alternative derivation of the
same quantity, leading to a simpler expression which is also calculable for
finite-sized matrices, away from the microscopic limit. We explicitly prove the
equivalence of the old and new results in the microscopic limit. The results
for finite-sized matrices illustrate the convergence towards the microscopic
limit. We compare the analytical results with dynamical random matrix
simulations, where various reweighting methods are used to circumvent the sign
problem. We discuss the pros and cons of these reweighting methods.Comment: 34 pages, 3 figures, references added, as published in JHE
Few-Shot Single-View 3-D Object Reconstruction with Compositional Priors
The impressive performance of deep convolutional neural networks in
single-view 3D reconstruction suggests that these models perform non-trivial
reasoning about the 3D structure of the output space. However, recent work has
challenged this belief, showing that complex encoder-decoder architectures
perform similarly to nearest-neighbor baselines or simple linear decoder models
that exploit large amounts of per category data in standard benchmarks. On the
other hand settings where 3D shape must be inferred for new categories with few
examples are more natural and require models that generalize about shapes. In
this work we demonstrate experimentally that naive baselines do not apply when
the goal is to learn to reconstruct novel objects using very few examples, and
that in a \emph{few-shot} learning setting, the network must learn concepts
that can be applied to new categories, avoiding rote memorization. To address
deficiencies in existing approaches to this problem, we propose three
approaches that efficiently integrate a class prior into a 3D reconstruction
model, allowing to account for intra-class variability and imposing an implicit
compositional structure that the model should learn. Experiments on the popular
ShapeNet database demonstrate that our method significantly outperform existing
baselines on this task in the few-shot setting
Evolution spatio-temporelle de la qualité physico-chimique de l’eau de l’estuaire du fleuve Comoé (Sud-est de la Côte d’ivoire)
Dans le but de faire une caractérisation physico-chimique de l’eau de l’estuaire du fleuve Comoé, une combinaison de méthodes d’analyses statistiques avec les données de la variabilité spatio-temporelle de la qualité de l’eau de l’estuaire a été faite. Les résultats de cette combinaison montrent l’existence de trois familles d’eaux : la première famille est représentée par les stations S1, S2, S3 et S4. Ces stations sont caractérisées par une faible minéralisation, une forte turbidité et des températures élevées. Ces stations sont riches en nitrates. La seconde famille, regroupe les stations S9 et S10. Ces stations sont caractérisées par une faible température, une forte transparence et peu minéralisées. La troisième famille regroupe les stations S5, S6, S7 et S8. Ces stations sont caractérisées par une richesse en phosphates et nitrites. La pollution la plus importante est observée, en général, pendant la saison des pluies. Cette étude a permis de ressortir également l’influence primordiale des variations saisonnières et des activités anthropiques sur la qualité des eaux de l’estuaire.Mots clés : qualité des eaux, paramètres physico-chimiques, estuaire du Comoé, Côte d’Ivoire
Systematic study of the SO(10) symmetry breaking vacua in the matrix model for type IIB superstrings
We study the properties of the space-time that emerges dynamically from the
matrix model for type IIB superstrings in ten dimensions. We calculate the free
energy and the extent of space-time using the Gaussian expansion method up to
the third order. Unlike previous works, we study the SO(d) symmetric vacua with
all possible values of d within the range , and observe clear
indication of plateaus in the parameter space of the Gaussian action, which is
crucial for the results to be reliable. The obtained results indeed exhibit
systematic dependence on d, which turns out to be surprisingly similar to what
was observed recently in an analogous work on the six-dimensional version of
the model. In particular, we find the following properties: i) the extent in
the shrunken directions is given by a constant, which does not depend on d; ii)
the ten-dimensional volume of the Euclidean space-time is given by a constant,
which does not depend on d except for d = 2; iii) The free energy takes the
minimum value at d = 3. Intuitive understanding of these results is given by
using the low-energy effective theory and some Monte Carlo results.Comment: 33 pages, 10 figures; minor corrections, reference added. arXiv admin
note: substantial text overlap with arXiv:1007.088
A practical solution to the sign problem in a matrix model for dynamical compactification
The matrix model formulation of superstring theory offers the possibility to
understand the appearance of 4d space-time from 10d as a consequence of
spontaneous breaking of the SO(10) symmetry. Monte Carlo studies of this issue
is technically difficult due to the so-called sign problem. We present a
practical solution to this problem generalizing the factorization method
proposed originally by two of the authors (K.N.A. and J.N.). Explicit Monte
Carlo calculations and large-N extrapolations are performed in a simpler matrix
model with similar properties, and reproduce quantitative results obtained
previously by the Gaussian expansion method. Our results also confirm that the
spontaneous symmetry breaking indeed occurs due to the phase of the fermion
determinant, which vanishes for collapsed configurations. We clarify various
generic features of this approach, which would be useful in applying it to
other statistical systems with the sign problem.Comment: 44 pages, 64 figures, v2: some minor typos correcte
Effect of Cyclooxygenase(COX)-1 and COX-2 inhibition on furosemide-induced renal responses and isoform immunolocalization in the healthy cat kidney
BACKGROUND: The role of cyclooxygenase(COX)-1 and COX-2 in the saluretic and renin-angiotensin responses to loop diuretics in the cat is unknown. We propose in vivo characterisation of isoform roles in a furosemide model by administering non-steroidal anti-inflammatory drugs (NSAIDs) with differing selectivity profiles: robenacoxib (COX-2 selective) and ketoprofen (COX-1 selective). RESULTS: In this four period crossover study, we compared the effect of four treatments: placebo, robenacoxib once or twice daily and ketoprofen once daily concomitantly with furosemide in seven healthy cats. For each period, urine and blood samples were collected at baseline and within 48 h of treatment starting. Plasma renin activity (PRA), plasma and urinary aldosterone concentrations, glomerular filtration rate (GFR) and 24 h urinary volumes, electrolytes and eicosanoids (PGE(2), 6-keto-PGF1(α,) TxB(2)), renal injury biomarker excretions [N-acetyl-beta-D-glucosaminidase (NAG) and Gamma-Glutamyltransferase] were measured. Urine volume (24 h) and urinary sodium, chloride and calcium excretions increased from baseline with all treatments. Plasma creatinine increased with all treatments except placebo, whereas GFR was significantly decreased from baseline only with ketoprofen. PRA increased significantly with placebo and once daily robenacoxib and the increase was significantly higher with placebo compared to ketoprofen (10.5 ± 4.4 vs 4.9 ± 5.0 ng ml(−1) h(−1)). Urinary aldosterone excretion increased with all treatments but this increase was inhibited by 75 % with ketoprofen and 65 % with once daily robenacoxib compared to placebo. Urinary PGE(2) excretion decreased with all treatments and excretion was significantly lower with ketoprofen compared to placebo. Urinary TxB(2) excretion was significantly increased from baseline only with placebo. NAG increased from baseline with all treatments. Immunohistochemistry on post-mortem renal specimens, obtained from a different group of cats that died naturally of non-renal causes, suggested constitutive COX-1 and COX-2 co-localization in many renal structures including the macula densa (MD). CONCLUSIONS: These data suggest that both COX-1 and COX-2 could generate the signal from the MD to the renin secreting cells in cats exposed to furosemide. Co-localization of COX isoenzymes in MD cells supports the functional data reported here. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1186/s12917-015-0598-z) contains supplementary material, which is available to authorized users
Hierarchy Theory of Evolution and the Extended Evolutionary Synthesis: Some Epistemic Bridges, Some Conceptual Rifts
Contemporary evolutionary biology comprises a plural landscape of multiple co-existent conceptual frameworks and strenuous voices that disagree on the nature and scope of evolutionary theory. Since the mid-eighties, some of these conceptual frameworks have denounced the ontologies of the Modern Synthesis and of the updated Standard Theory of Evolution as unfinished or even flawed. In this paper, we analyze and compare two of those conceptual frameworks, namely Niles Eldredge’s Hierarchy Theory of Evolution (with its extended ontology of evolutionary entities) and the Extended Evolutionary Synthesis (with its proposal of an extended ontology of evolutionary processes), in an attempt to map some epistemic bridges (e.g. compatible views of causation; niche construction) and some conceptual rifts (e.g. extra-genetic inheritance; different perspectives on macroevolution; contrasting standpoints held in the “externalism–internalism” debate) that exist between them. This paper seeks to encourage theoretical, philosophical and historiographical discussions about pluralism or the possible unification of contemporary evolutionary biology
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