Historical Aspects of the Chemical Bond. Chemical Relationality versus Physical Objectivity

Chemists have always defined the properties of materials on the basis of the changes observed when they reacted with other substances. Whereas this approach led chemists to relational concepts such as affinity, acid, and oxidant, physicists made measurements of objects they considered unchanged, determining their mass, charge, dipole moment, etc. In the middle of the 18th century, the Jesuit Josip Ruder Bocovi started thinking about the way in which atoms might be present in crystals, introducing a new concept according to which atoms in condensed phases represented punctual centres of attracting and repelling forces. Josef Loschmidt became aware of these ideas through the philosopher J. F. Herbart, and it is to Loschmidt that we owe the first representation of bonds as atomic spheres penetrating one another. The term quantum chemistry was first used by the physicist Arthur Erich Haas, who was born in Brno. However, Hans Hellmann (1903–1938) was the true founder of quantum chemistry. Hellmann, who was shot in Moscow in 1938, was the first person to realize the quantum-physical effect that leads to the chemical bond. In the 1960s K. Ruedenberg and others took theory a stage further when – thanks to the concept of the localized electron pair – they realized that the different approaches to the phenomenon of the chemical bond taken by chemists and physicists were largely comparable. This made it possible to bring the differing standpoints largely into line with one another.     

Technical Procedures for the Syntheses of Carotenoids and Related Compounds from 6-Oxo-isophorone: Syntheses of (3R,3′R)-Zeaxanthin. Part I

Starting from the readily available, optically active (4R)-4-hydroxy-2,2,6-trimethylcyclohexanone ( 1 ), a new technical synthesis of (3R,3′R)-zeaxanthin is described. According to a 2(C₉ + C₆) + C₁₀ = C₄₀ construction scheme, the ketone 1 was first transformed with (E)-3-methylpent-2-en-4-yn-1-ol ( 5 ) into a C₁₅-intermediate which, by a three-step sequence, could be converted into the known olefinic C₁₅-Wittig salt 4 . Optimized conditions for the final Wittig reaction of 4 with the C₁₀-dialdehyde 3 are discussed. Based on 1 , the overall yield of the entire technical process is ca. 40%.     

Ligand requirements for glmS ribozyme self-cleavage

Natural RNA catalysts (ribozymes) perform essential reactions in biological RNA processing and protein synthesis, whereby catalysis is intrinsic to RNA structure alone or in combination with metal ion cofactors. The recently discovered glmS ribozyme is unique in that it functions as a glucosamine-6-phosphate (GlcN6P)-dependent catalyst believed to enable "riboswitch" regulation of amino-sugar biosynthesis in certain prokaryotes. However, it is unclear whether GlcN6P functions as an effector or coenzyme to promote ribozyme self-cleavage. Herein, we demonstrate that ligand is absolutely requisite for glmS ribozyme self-cleavage activity. Furthermore, catalysis both requires and is dependent upon the acid dissociation constant (pKa) of the amine functionality of GlcN6P and related compounds. The data demonstrate that ligand is integral to catalysis, consistent with a coenzyme role for GlcN6P and illustrating an expanded capacity for biological RNA catalysis.     

Uncountable Strongly Surjective Linear Orders

Order - We call a linear order L strongly surjective if whenever K is a suborder of L then there is a surjective f : L → K so that x ≤ y implies f(x) ≤ f(y). We prove various...     

A tall space with a small bottom

We introduce a general method of constructing locally compact scattered spaces from certain families of sets and then, with the help of this method, we prove that if , then there is such a space of height with only many isolated points. This implies that there is a locally compact scattered space of height with isolated points in ZFC, solving an old problem of the first author.

     

The Collins–Roscoe mechanism and <Emphasis Type="Italic">D</Emphasis>-spaces

We prove that if a space X is well ordered (αA), or linearly semi-stratifiable, or elastic then X is a D-space.     

Comparison of simulations and data from a seismo-acoustic tank experiment

A tank experiment was carried out to investigate underwater sound propagation over an elastic bottom in flat and sloping configurations. The purpose of the experiment was to evaluate range-dependent propagation models with high-quality experimental data. The sea floor was modeled as an elastic medium by a polyvinyl chloride slab. The relatively high rigidity of the slab requires accounting for shear waves in this environment. Acoustic measurements were obtained along virtual arrays in the water column using a robotic apparatus. Elastic parabolic equation solutions are in excellent agreement with data.     

Decompositions of edge-coloured infinite complete graphs into monochromatic paths II

We prove that given an edge colouring of an infinite complete graph with finitely many colours, one can partition the vertices of the graph into disjoint monochromatic paths of different colours. This answers a question of R. Rado from 1978.     

Elementary submodels in infinite combinatorics

The use of elementary submodels is a simple but powerful method to prove theorems, or to simplify proofs in infinite combinatorics. First we introduce all the necessary concepts of logic, then we prove classical theorems using elementary submodels. We also present a new proof of Nash-Williams’s theorem on cycle decomposition of graphs, and finally we improve a decomposition theorem of Laviolette concerning bond-faithful decompositions of graphs.