Stereochemicai study of 7-aryl-1,7,8,8a-tetrahydro-3(2H)indolizinones by1H and13C NMR

Stereochemistry of 7-aryl-1,7,8,8a-tetrahydro-3(2H)-indolizinones was studied by¹H and¹³C NMR. Complete assignment of¹H NMR signals and analysis of¹H-¹H coupling constants were performed using the iterative PANIC program. Values of³ J _6,7,³ J _7,8endo, and⁴ J _5,7 allow one to unambiguously identify the correspondingexo- andendo-stereoisomers. For stereoisomers with exo-orientation of H(7), complete assignment of¹³C NMR signals was performed on the basis of analysis of the¹³C-¹H coupling constants using two dimensional heteronuclear shift-correlating spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 591–593, March, 1996.     

Infrared investigation of aluminum- and chromium-substituted magnetites and of the lacunar spinels resulting from their oxidation

When Fe³⁺ ions are substituted by aluminum or chromium on magnetite octahedral sites, the ir spectrum shows the conversion of an inverse spinel to a normal spinel. Both broad bands of magnetite are gradually replaced by the four characteristic bands of normal spinels II–III. They are also observed for solid solutions, FeCr₂O₄FeAl₂O₄, with, however, a further band at 780 cm^?1 which may be assigned to Al³⁺ ions on tetrahedral sites. Low-temperature (<400°C) oxidation of these compounds whose sizes are less than 2000 Å results in lacunar spinels III–III. The ir spectrum of these solids is characterized by two absorption bands (as for inverse spinels II–III) except for compounds close to pure γFe₂O₃ in which an order of vacancies could be put in evidence.     

Natural spline functions,their associated eigenvalue problem

Summary We consider the problem of studying the behaviour of the eigenvalues associated with spline functions with equally spaced knots. We show that they are wherem is the order of the spline andn, the number of knots.This result is of particular interest to prove optimality properties of the Generalized Cross-Validation Method and had been conjectured by Craven and Wahba in a recent paper.     

Prescriptions and Ingredients for Controlled CC Bond Formation with Organometallic Reagents. New synthetic methods (5)

Merits and drawbacks of known carbon-carbon linking procedures are outlined. Two novel methods are discussed in some detail: the copper-catalyzed alkylation of Grignard reagents and reactions with allylpotassium compounds. Both methods provide a very efficient access to saturated, unsaturated, as well as functionally substituted hydrocarbons and moreover permit an astonishing degree of regio- and stereoselective control of olefin synthesis.     

The structure of 1-formyl-3-phenyl-Δ-pyrazoline in the gas phase (DFT calculations), in solution (NMR) and in the solid state (X-ray crystallography)

The molecular structure of 1-formyl-3-phenyl-Δ²-pyrazoline was determined by X-ray crystallography (triclinic, P-1). The geometry thus obtained was compared with that obtained by DFT calculations. The GIAO method was used to calculate absolute shieldings, which agree conveniently with those measured by ¹³C and ¹⁵N NMR. The title compound appears to be an essentially planar molecule.     

In-capillary micro solid-phase extraction and capillary electrophoresis separation of heterocyclic aromatic amines with nanospray mass spectrometric detection

A miniaturised technique to analyse and detect heterocyclic aromatic amines (HAs) using micro solid-phase extraction (SPE) coupled on-line (in-capillary) to capillary electrophoresis (CE) separation with nanospray (nESI) mass spectrometry (MS) detection has been developed. HAs are mutagenic and carcinogenic compounds formed at low levels in protein-rich food during cooking. Due to the low concentrations of HAs and the high complexity of the matrix in which they exist, sensitive and selective analytical methods are required for quantification. SPE was performed on a packed bed of C₁₈ particles inside the CE capillary, which minimised the dead volume. The on-line coupling of SPE, CE and nESI-MS reduced the time for extraction and identification to less than half an hour, which will allow for screening of several samples per day. The new technique provides short analysis time, low sample and solvent consumption, and HAs in standard solutions were easily detected at 12–17 fmol injections, and in spiked urine samples at 750–810 fmol injections.     

Solvent-induced electronic spectral shifts: Benzene·Arn revisited

Just what can be learned about cluster dynamics (and, more generally, about solvation dynamics) from spectral studies of small clusters that have been doped with a chromophore is still an open question. In the present work we suggest a novel procedure for calculating the shift in the electronic absorption spectrum of a chromophore deriving from the attachment to or the incorporation in a cluster. The particular system of interest here is benzene·Ar _n , for which experimental results are readily available although their interpretation has been a point of controversy. In addition, since the present formalism is equally applicable to a chromophore isolated in a bulk phase (either liquid or solid), we are able to venture an explanation for the apparent observation that the spectral shift of cluster-isolated benzene does not approach the asymptotic values characteristic of the bulk-isolated species.     

Orthmodular lattices whose MacNeille completions are not orthomodular

The only known example of an orthomodular lattice (abbreviated: OML) whose MacNeille completion is not an OML has been noted independently by several authors, see Adams [1], and is based on a theorem of Ameniya and Araki [2]. This theorem states that for an inner product space V, if we consider the ortholattice ?(V,⊥) = {A \( \subseteq \) V: A = A ^⊥⊥} where A ^⊥ is the set of elements orthogonal to A, then ?(V,⊥) is an OML if and only if V is complete. Taking the orthomodular lattice L of finite or confinite dimensional subspaces of an incomplete inner product space V, the ortholattice ?(V,⊥) is a MacNeille completion of L which is not orthomodular. This does not answer the longstanding question Can every OML be embedded into a complete OML? as L can be embedded into the complete OML ?(V,⊥), where V is the completion of the inner product space V. Although the power of the Ameniya-Araki theorem makes the preceding example elegant to present, the ability to picture the situation is lost. In this paper, I present a simpler method to construct OMLs whose Macneille completions are not orthomodular. No use is made of the Ameniya-Araki theorem. Instead, this method is based on a construction introduced by Kalmbach [7] in which the Boolean algebras generated by the chains of a lattice are glued together to form an OML. A simple method to complete these OMLs is also given. The final section of this paper briefly covers some elementary properties of the Kalmbach construction. I have included this section because I feel that this construction may be quite useful for many purposes and virtually no literature has been written on it.     

Search

This paper reviews the theory of search. The main viewpoint is statistical but considerable space is spent on connections with other fields such as logic and optimisation. Three primitive ideas dominate: consistency, entropy, and Bayes' methods. The theory of screening provides one of the central examples and there is a section on nonsequential random search deriving from the work of Renyi. The game of Bulls and Cows provides a motivating example for both sequential and nonsequential algorithms.