Formal total syntheses of aspidosperma alkaloids via a novel and general synthetic pathway based on an intramolecular Heck cyclization

Cyclizations of bicyclic amides via an intramolecular Heck reaction followed by an oxidation reaction generate tricyclic spirocyclohexadienones. From these compounds, tetracyclic ketones can be synthesized to provide useful intermediates for the synthesis of indole alkaloids.     

Impedance Response of a Thin Film on an Electrode: Deciphering the Influence of the Double Layer Capacitance

The different contributions of the interfacial capacitance are identified in the case of passive materials or thin protective coatings deposited on the electrode surface. The method is based on a graphical analysis of the EIS results to determine both the passive-film capacitance in the high-frequency domain and the double-layer capacitance in the low-frequency domain. The proposed analysis is shown to be independent of the physicochemical origins of the frequency dispersion of the interfacial capacitances which results, from an analysis point of view of the experimental results, in the use of a constant-phase element However, for a correct evaluation of the thin-film properties such as its thickness, the high-frequency data must be corrected for the double-layer contribution. In particular, it is shown that if the double-layer capacitance gives a frequency-dispersed response, it is necessary to correct the high-frequency part for the double-layer constant-phase elements. This is first demonstrated on synthetic data and then used for the determination of the thickness of thin oxide film formed on Al in neutral pH solution.     

Isolation of lanthanides from spent nuclear fuel by means of high performance ion chromatography (HPIC) prior to mass spectrometric analysis

Pure and complete fractions of neodymium, samarium, europium, gadolinium and dysprosium were isolated by means of high performance ion chromatography, using a cation exchange column and gradient elution with alpha-hydroxyisobutyric acid solutions (α-HIBA). Intermediate precision and robustness of the isolation method was investigated, identifying eluent pH as the most important parameter. Investigation of the elution behaviour of the most important fission and activation products and actinides indicated that preventing the accumulation of cesium on the cation exchange column required further isocratic elution with a higher concentrated α-HIBA solution after elution of the lanthanides. A sample matrix free of carbon was achieved by means of acid digestion, followed by UV photo-oxidation, resulting in samples suitable for mass spectrometric analysis.

     

Lecture Hall Partitions II

For a non-decreasing integer sequence a=(a₁,...,a_n) we define L_a to be the set of n-tuples of integers = (₁,...,_n) satisfying . This generalizes the so-called lecture hall partitions corresponding to a_i=i and previously studied by the authors and by Andrews. We find sequences a such that the weight generating function for these a-lecture hall partitions has the remarkable form In the limit when n tends to infinity, we obtain a family of identities of the kind the number of partitions of an integer m such that the quotient between consecutive parts is greater than is equal to the number of partitions of m into parts belonging to the set P, for certain real numbers and integer sets P. We then underline the connection between lecture hall partitions and Ehrhart theory and discuss some reciprocity results.     

Enumeration of three-dimensional convex polygons

A self-avoiding polygon (SAP) on a graph is an elementary cycle. Counting SAPs on the hypercubic lattice ℤ ^d withd≥2, is a well-known unsolved problem, which is studied both for its combinatorial and probabilistic interest and its connections with statistical mechanics. Of course, polygons on ℤ ^d are defined up to a translation, and the relevant statistic is their perimeter. A SAP on ℤ ^d is said to beconvex if its perimeter is “minimal”, that is, is exactly twice the sum of the side lengths of the smallest hyper-rectangle containing it. In 1984, Delest and Viennot enumerated convex SAPs on the square lattice [6], but no result was available in a higher dimension. We present an elementar approach to enumerate convex SAPs in any dimension. We first obtain a new proof of Delest and Viennot's result, which explains combinatorially the form of the generating function. We then compute the generating function for convex SAPs on the cubic lattice. In a dimension larger than 3, the details of the calculations become very cumbersome. However, our method suggests that the generating function for convex SAPs on ℤ ^d is always a quotient ofdifferentiably finite power series.     

Decreasing Subsequences in Permutations and Wilf Equivalence for Involutions

In a recent paper, Backelin, West and Xin describe a map φ^* that recursively replaces all occurrences of the pattern k... 21 in a permutation σ by occurrences of the pattern (k−1)... 21 k. The resulting permutation φ^*(σ) contains no decreasing subsequence of length k. We prove that, rather unexpectedly, the map φ^* commutes with taking the inverse of a permutation. In the BWX paper, the definition of φ^* is actually extended to full rook placements on a Ferrers board (the permutations correspond to square boards), and the construction of the map φ^* is the key step in proving the following result. Let T be a set of patterns starting with the prefix 12... k. Let T′ be the set of patterns obtained by replacing this prefix by k... 21 in every pattern of T. Then for all n, the number of permutations of the symmetric group _n that avoid T equals the number of permutations of _n that avoid T′. Our commutation result, generalized to Ferrers boards, implies that the number of involutions of _n that avoid T is equal to the number of involutions of _n avoiding T′, as recently conjectured by Jaggard. Both authors were partially supported by the European Commission's IHRP Programme, grant HPRN-CT-2001-00272, “Algebraic Combinatorics in Europe”     

Factor probabilistic distance clustering (FPDC): a new clustering method

Factor clustering methods have been developed in recent years thanks to improvements in computational power. These methods perform a linear transformation of data and a clustering of the transformed data, optimizing a common criterion. Probabilistic distance (PD)-clustering is an iterative, distribution free, probabilistic clustering method. Factor PD-clustering (FPDC) is based on PD-clustering and involves a linear transformation of the original variables into a reduced number of orthogonal ones using a common criterion with PD-clustering. This paper demonstrates that Tucker3 decomposition can be used to accomplish this transformation. Factor PD-clustering alternatingly exploits Tucker3 decomposition and PD-clustering on transformed data until convergence is achieved. This method can significantly improve the PD-clustering algorithm performance; large data sets can thus be partitioned into clusters with increasing stability and robustness of the results. Real and simulated data sets are used to compare FPDC with its main competitors, where it performs equally well when clusters are elliptically shaped but outperforms its competitors with non-Gaussian shaped clusters or noisy data.     

Analysis of grid file algorithms

Grid file algorithms were suggested in [12] to provide multi-key access to records in a dynamically growing file. We specify here two algorithms and derive the average sizes of the corresponding directories. We provide an asymptotic analysis. The growth of the indexes appears to be non-linear for uniform distributions:O(v ^c ) orO(v ), wherec=1+b^–1, =1+(s-1)/(sb+1),s is the number of attributes being used,v the file size, andb the page capacity of the system. Finally we give corresponding results for biased distributions and compare transient phases.     

Triades et familles de courbes gauches

Sans résumé Received: 3 April 1998 / in final form: 16 December 1998