Recent advances in the asymmetric catalytic synthesis of chiral 3-hydroxy and 3-aminooxindoles and derivatives: Medicinally relevant compounds

Several oxindole derivatives, of natural or synthetic origin, have been identified as medicinally appealing compounds, with a plethora of bioactivities reported. Chiral 3-hydroxy and 3-aminooxindole scaffolds have captured the attention of several research groups, due to their importance in drug discovery. In this review, we systematically address the wide variety of asymmetric catalytic methodologies employed in the preparation of these relevant chiral scaffolds, present in many biologically active compounds and/or natural products. Special focus will be given to the nature of the catalyst used.     

The computation of characteristic classes of lattice gauge fields

AGL(p,C)-valued lattice gauge fieldu on a simplicial complex determines a principalGL(p,C)-bundle if the plaquette products are sufficiently small with respect to the maximum distortion coefficient of the transporters. A representative cocyclec _q for theq ^th Chern class of can be computed on each 2q-simplex by takingc _q() to be the intersection number of a certain singular 2q-cubeM with a Schubert-type variety _q in the space of allp×p matrices. This reduces to the solution of polynomial equations with coefficients coming fromu and thus avoids numerical integration or cooling-type procedures. An application of this method is suggested for the computation of the topological charge of anSU(3)-valued lattice gauge field on a 4-complex.Partially supported by NSF grant DMS 8607168Partially supported by PSC-CUNY and by NSF grant DMS 8805485     

Monte Carlo approximation through Gibbs output in generalized linear mixed models

Geyer (J. Roy. Statist. Soc. 56 (1994) 291) proposed Monte Carlo method to approximate the whole likelihood function. His method is limited to choosing a proper reference point. We attempt to improve the method by assigning some prior information to the parameters and using the Gibbs output to evaluate the marginal likelihood and its derivatives through a Monte Carlo approximation. Vague priors are assigned to the parameters as well as the random effects within the Bayesian framework to represent a non-informative setting. Then the maximum likelihood estimates are obtained through the Newton Raphson method. Thus, out method serves as a bridge between Bayesian and classical approaches. The method is illustrated by analyzing the famous salamander mating data by generalized linear mixed models.     

A directed topic model applied to call center improvement

We propose subject matter expert refined topic (SMERT) allocation, a generative probabilistic model applicable to clustering freestyle text. SMERT models are three‐level hierarchical Bayesian models in which each item is modeled as a finite mixture over a set of topics. In addition to discrete data inputs, we introduce binomial inputs. These ‘high‐level’ data inputs permit the ‘boosting’ or affirming of terms in the topic definitions and the ‘zapping’ of other terms. We also present a collapsed Gibbs sampler for efficient estimation. The methods are illustrated using real world data from a call center. Also, we compare SMERT with three alternative approaches and two criteria. Copyright © 2015 John Wiley & Sons, Ltd.     

High resolution dynamic cardiac MRI using partial separability of spatiotemporal signals with a novel sampling scheme

The partial separability (PS) of spatiotemporal signals has been exploited to accelerate dynamic cardiac MRI by sampling two datasets (training and imaging datasets) without breath-holding or ECG triggering. According to the theory of partially separable functions, the wider the range of spatial frequency components covered by the training dataset, the more accurate the temporal constraint imposed by the PS model. Therefore, it is necessary to develop a new sampling scheme for the PS model in order to cover a wider range of spatial frequency components. In this paper, we propose the use of radial sampling trajectories for collecting the training dataset and Cartesian sampling trajectories for collecting the imaging dataset. In vivo high resolution cardiac MRI experiments demonstrate that the proposed data sampling scheme can significantly improve the image quality. The image quality using the PS model with the proposed sampling scheme is comparable to that of a commercial method using retrospective cardiac gating and breath-holding. The success of this study demonstrates great potential for high-quality, high resolution dynamic cardiac MRI without ECG gating or breath-holding through use of the PS model and the novel data sampling scheme.     

Soft X‐ray absorption spectroscopy and resonant inelastic X‐ray scattering spectroscopy below 100 eV: probing first‐row transition‐metal M‐edges in chemical complexes

X‐ray absorption and scattering spectroscopies involving the 3d transition‐metal K‐ and L‐edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M‐edges, which are below 100 eV. Synchrotron‐based X‐ray sources can have higher energy resolution at M‐edges. M‐edge X‐ray absorption spectroscopy (XAS) and resonant inelastic X‐ray scattering (RIXS) could therefore provide complementary information to K‐ and L‐edge spectroscopies. In this study, M_2,3‐edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M_2,3‐edge RIXS on NiO, NiF₂ and two other covalent complexes have been performed and different d–d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M‐edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high‐sensitivity and high‐resolution superconducting tunnel junction X‐ray detectors below 100 eV is also illustrated and discussed.     

Ultrasonic absorption in polymer gel dosimeters

Ultrasonic absorption in polymer gel dosimeters was investigated. An ultrasonic interferometer was used to study the frequency (f) dependence of the absorption coefficient (alpha) in a polyacrylamide gel dosimeter (PAG) in the frequency range 5-20 MHz. The frequency dependence of ultrasonic absorption deviated from that of an ideal viscous fluid. The presence of relaxation mechanisms was evidenced by the frequency dependence of alpha/f(2) and the dispersion in ultrasonic velocity. It was concluded that absorption in polymer gel dosimeters is due to a number of relaxation processes which may include polymer-solvent interactions as well as relaxation due to motion of polymer side groups.The dependence of ultrasonic absorption on absorbed dose and formulation was also investigated in polymer gel dosimeters as a function of pH and chemical composition. Changes in dosimeter pH and chemical composition resulted in a variation in ultrasonic dose response curves. The observed dependence on pH was considered to be due to pH induced modifications in the radiation yield while changes in chemical composition resulted in differences in polymerisation kinetics.     

Universality properties of Gelfand–Tsetlin patterns

A standard Gelfand–Tsetlin pattern of depth n is a configuration of particles in ${\{1,\ldots,n\} \times \mathbb{R}}$ . For each ${r \in \{1, \ldots, n\}, \{r\} \times \mathbb{R}}$ is referred to as the rth level of the pattern. A standard Gelfand–Tsetlin pattern has exactly r particles on each level r, and particles on adjacent levels satisfy an interlacing constraint. Probability distributions on the set of Gelfand–Tsetlin patterns of depth n arise naturally as distributions of eigenvalue minor processes of random Hermitian matrices of size n. We consider such probability spaces when the distribution of the matrix is unitarily invariant, prove a determinantal structure for a broad subclass, and calculate the correlation kernel. In particular we consider the case where the eigenvalues of the random matrix are fixed. This corresponds to choosing uniformly from the set of Gelfand–Tsetlin patterns whose nth level is fixed at the eigenvalues of the matrix. Fixing ${q_n \in \{1,\ldots,n\}}$ , and letting n → ∞ under the assumption that ${\frac{q_n}n \to \alpha \in (0, 1)}$ and the empirical distribution of the particles on the nth level converges weakly, the asymptotic behaviour of particles on level q _n is relevant to free probability theory. Saddle point analysis is used to identify the set in which these particles behave asymptotically like a determinantal random point field with the Sine kernel.     

Superefficient drift estimation on the Wiener space

In the framework of a nonparametric functional estimation for the drift of a Brownian motion $X_t$ we construct Stein type estimators of the form $X_t+D_t\log F$ which are superefficient when $\sqrt{F}$ is a superharmonic functional on the Wiener space for the Malliavin derivative D. To cite this article: N. Privault, A. Réveillac, C. R. Acad. Sci. Paris, Ser. I 343 (2006).