Theoretical implications involved in the DDRP method

The aim of this paper is to prove that safe success in finding reaction paths (RPs) can only be expected from global path-determining methods. Some extensions of the mathematical arguments leading to the introduction of the DDRP (dynamically defined reaction path) method have been sketched. Four cases involving relaxation of analyticity, variability of the gradient field, minimum energy (reaction) paths (MEPs) and golf pocket holes on the potential energy surface (PES), and the rather strange consequences of the main theorem of the DDRP method giving a rigorous mathematical basis to chemical intuition in reaction kinetics have been discussed. The discussions show that the DDRP method - when changing the conditions and parameters - may, in essence, involve all other global methods. It has been shown that the DDRP method works in a stable way even for non-analytic though smooth energy functions; moreover, the gradient field can be replaced by other vector fields resulting in better convergence to the reaction path. As a by-product, the question of the existence of MEPs can safely be handled and golf pocket holes are constructed on the PES in order to prove that local methods have chance to search faithfully the RPs in complicated systems only if the energy function can be restored from its arbitrarily small pieces.This work was presented in parts at the 8th International Congress of Quantum Chemistry, Prague, Czech Republic, June 19–23,1994; Addendum to the Book of Abstracts of the 8ICQC: P/I-129.     

Tensor products of contexts and complete lattices

Although the categoryCLC of complete lattices and complete homomorphisms does not possess arbitrary coproducts, we show that the tensor product introduced by Wille has the universal property of coproducts for so-called distributing families of morphisms (and only for these). As every family of morphisms into a completely distributive lattice is distributing, this includes the known fact that in the category of completely distributive lattices, arbitrary coproducts exist and coincide with the tensor products. Since the definition of tensor products is based on the notion of contexts and their concept lattices, many results on tensor products extend from complete lattices to contexts. Thus we introduce two kinds of tensor products for arbitrary families of contexts, a partial and a complete one, and establish universal properties of these tensor products.Presented by B. Jonsson.     

Discrete groups of slow subgroup growth

It is known that the subgroup growth of finitely generated linear groups is either polynomial or at least $n^{\frac{{\log n}}{{\log \log n}}} $ . In this paper we prove the existence of a finitely generated group whose subgroup growth is of type $n^{\frac{{\log n}}{{(\log \log n)^2 }}} $ . This is the slowest non-polynomial subgroup growth obtained so far for finitely generated groups. The subgroup growth typen ^logn is also realized. The proofs involve analysis of the subgroup structure of finite alternating groups and finite simple groups in general. For example, we show there is an absolute constantc such that, ifT is any finite simple group, thenT has at mostn ^{c logn} subgroups of indexn.     

Synthesis and structure of a dithioether-substituted butene-2-olide-4-ylidene-4 cobalt carbonyl complex

The complex (1) has been prepared and its structure determined. Complex1 is the first stable thioether derivative of a metal carbonyl containing only cobalt as metal. It crystallizes in the monoclinic P2₁/c space group, witha = 13.975( 4 ),b = 11.363( 3 ),c = 14.686(2)A, = 112.25(2)°,V = 2158.5(7)A³.Z = 4. The solution using direct methods and the anisotropic refinement of all nonhydrogen atoms led toR = 0.039,wR = 0.041 for 3296 reflections with F> 4.0(F) Analogous but less stable complexes are formed with 1,6-diphenyl-2,5-dithiahexane and the crown thioether 1,4,7-trithiacyclonane, the latter functioning either as a bidenlate or a tridentate ligand.     

Experimental determination of the flame expansion factor

The flame expansion factor (ratio of volumes of flame gases before and after burning) has been determined by mercury vapour introduction. The method is based on the determination of atomic concentration ratio in the flame and the flameless gas jet using the same sample introduction rate. A good agreement has been found between the expansion factors determined by the proposed method and those calculated by the gas law.     

Flow-through optical fiber sensor for automatic sulfide determination in waters by multisyringe flow injection analysis using solid-phase reflectometry

A software-controlled flow-through optical fiber diffuse reflectance sensor capitalized on the implementation of disk-based solid-phase pre-concentration schemes in a multisyringe flow injection analysis (MSFIA) set-up is proposed for the trace determination of sulfide in environmental waters and wastewaters. The fully automated flowing methodology is based on Fischer's coupling reaction of sulfide with N,N-dimethyl-p-phenylenediamine (DMPD) in the presence of Fe(iii) as oxidizing reagent in a 0.5 M HCl medium. The on-line generated methylene blue dye is subsequently delivered downstream to a dedicated optode cell furnished with an octadecyl-chemically modified (C(18)) disk, while continuously recording the diffuse reflectance spectrum of the pre-concentrated compound. A double regeneration protocol is finally executed to warrant minimum background noise and negligible baseline. Under the optimized chemical and hydrodynamic conditions, the optosensing MSFIA method features coefficients of variation better than 0.7%(n= 10) at 50 microg l(-1) concentration, a linear working range of 20-200 microg l(-1) sulfide, a 3sigma(blank) detection limit of 2.9 microg l(-1) sulfide and an injection throughput of 8 h(-1) for a pre-concentration sample volume of 2.9 ml. The interfacing of the robust and versatile multisyringe flow injection-based optode with a plug-in spectrophotometer furnished with a light emitting diode assures the miniaturization of the overall flow analyzer, which is, thus, readily adaptable to real-time monitoring schemes. The potential of the multisyringe flow method was assessed via the determination of sulfide traces in water samples of different complexity (namely, freshwater, seawater and wastewater).     

Synthesis of vinca alkaloids and related compounds. 100. Stereoselective oxidation reactions of compounds with the aspidospermane and quebrachamine ring system. First synthesis of some alkaloids containing the epoxy ring

The first syntheses of the alkaloids (-)-mehranine (3), (+)-voaphylline/conoflorine (4), (+)-N(a)-methylvoaphylline/hecubine (5), and (-)-lochnericine (2) were achieved by stereoselective epoxidation starting from (-)-tabersonine (1), through intermediates with the aspidospermane and quebrachamine skeleton.