1H and 13C NMR assignments of abietane diterpenes from Aegiphila lhotzkyana

An NMR study of one new and several known abietane diterpenes isolated from the roots of Aegiphila lhotzkyana is described. In addition to 1D NMR, several 2D shift‐correlated NMR pulse sequences (¹H–¹H‐COSY, NOESY, HMQC and HMBC) were used to establish all the structures, and unambiguously perform the ¹H and ¹³C chemical shift assignments of the new natural diterpene and three derivatives, the NMR data for which have not been reported previously. Revision of current data assignment for teuvincenone H is also suggested. Copyright © 2003 John Wiley & Sons, Ltd.     

π1-classification of real arrangements with up to eight lines

One of the open questions in the geometry of line arrangements is to what extent does the incidence lattice of an arrangement determine its fundamental group. Line arrangements of up to 6 lines were recently classified by K.M. Fan (Michigan Math. J. 44(2) (1997) 283), and it turns out that the incidence lattice of such arrangements determines the projective fundamental group. We use actions on the set of wiring diagrams, introduced in (Garber et al. (J. Knot Theory Ramf.), to classify real arrangements of up to 8 lines. In particular, we show that the incidence lattice of such arrangements determines both the affine and the projective fundamental groups.     

Asymptotic properties of computationally efficient alternative estimators for a class of multivariate normal models

Parameters of Gaussian multivariate models are often estimated using the maximum likelihood approach. In spite of its merits, this methodology is not practical when the sample size is very large, as, for example, in the case of massive georeferenced data sets. In this paper, we study the asymptotic properties of the estimators that minimize three alternatives to the likelihood function, designed to increase the computational efficiency. This is achieved by applying the information sandwich technique to expansions of the pseudo-likelihood functions as quadratic forms of independent normal random variables. Theoretical calculations are given for a first-order autoregressive time series and then extended to a two-dimensional autoregressive process on a lattice. We compare the efficiency of the three estimators to that of the maximum likelihood estimator as well as among themselves, using numerical calculations of the theoretical results and simulations.     

A robust and efficient adaptive reweighted estimator of multivariate location and scatter

This article proposes a reweighted estimator of multivariate location and scatter, with weights adaptively computed from the data. Its breakdown point and asymptotic behavior under elliptical distributions are established. This adaptive estimator is able to attain simultaneously the maximum possible breakdown point for affine equivariant estimators and full asymptotic efficiency at the multivariate normal distribution. For the special case of hard-rejection weights and the MCD as initial estimator, it is shown to be more efficient than its non-adaptive counterpart for a broad range of heavy-tailed elliptical distributions. A Monte Carlo study shows that the adaptive estimator is as robust as its non-adaptive relative for several types of bias-inducing contaminations, while it is remarkably more efficient under normality for sample sizes as small as 200.     

Reliability and expectation bounds for coherent systems with exchangeable components

Sharp upper and lower bounds are obtained for the reliability functions and the expectations of lifetimes of coherent systems based on dependent exchangeable absolutely continuous components with a given marginal distribution function, by use of the concept of Samaniego's signature. We first show that the distribution of any coherent system based on exchangeable components with absolutely continuous joint distribution is a convex combination of distributions of order statistics (equivalent to the k-out-of-n systems) with the weights identical with the values of the Samaniego signature of the system. This extends the Samaniego representation valid for the case of independent and identically distributed components. Combining the representation with optimal bounds on linear combinations of distribution functions of order statistics from dependent identically distributed samples, we derive the corresponding reliability and expectation bounds, dependent on the signature of the system and marginal distribution of dependent components. We also present the sequences of exchangeable absolutely continuous joint distributions of components which attain the bounds in limit. As an application, we obtain the reliability bounds for all the coherent systems with three and four exchangeable components, expressed in terms of the parent marginal reliability function and specify the respective expectation bounds for exchangeable exponential components, comparing them with the lifetime expectations of systems with independent and identically distributed exponential components.     

Continuous modified Newton’s-type method for nonlinear operator equations

A nonlinear operator equation F(x)=0, F:H→H, in a Hilbert space is considered. Continuous Newton’s-type procedures based on a construction of a dynamical system with the trajectory starting at some initial point x ₀ and becoming asymptotically close to a solution of F(x)=0 as t→+∞ are discussed. Well-posed and ill-posed problems are investigated. Received: June 29, 2001; in final form: February 26, 2002?Published online: February 20, 2003 This paper was finished when AGR was visiting Institute for Theoretical Physics, University of Giessen. The author thanks DAAD for support     

Liquid-phase chlorination ofC-chlorovinylsilanes

Liquid-phase chlorination of a number of chloro(chlorovinyl)methylsilanes was investigated. A number of novelC-chlorosilanes were characterized by IR and¹H NMR spectra. Some regularities of these reactions were determined; correlations between the structure of chloro(chlorovinyl)methylsilanes and their reactivities were identified.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2256–2260, November, 1995.     

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HAC estimation and strong linearity testing in weak ARMA models

In the framework of ARMA models, we consider testing the reliability of the standard asymptotic covariance matrix (ACM) of the least-squares estimator. The standard formula for this ACM is derived under the assumption that the errors are independent and identically distributed, and is in general invalid when the errors are only uncorrelated. The test statistic is based on the difference between a conventional estimator of the ACM of the least-squares estimator of the ARMA coefficients and its robust HAC-type version. The asymptotic distribution of the HAC estimator is established under the null hypothesis of independence, and under a large class of alternatives. The asymptotic distribution of the proposed statistic is shown to be a standard χ² under the null, and a noncentral χ² under the alternatives. The choice of the HAC estimator is discussed through asymptotic power comparisons. The finite sample properties of the test are analyzed via Monte Carlo simulation.