Breakdown of symmetry in reversible systems

We review results on local bifurcations of codimension 1 in reversible systems (flows and diffeomorphisms) which lead to the birth of attractor-repeller pairs from symmetric equilibria (for flows) or periodic points (for diffeomorphisms).     

Efficient methods to study phase equilibria in multinary aqueous systems

We report the results of developing efficient universal isothermal methods for the determination of compositions of all phases (several solid phases and a liquid) involved in invariant equilibria in multicomponent aqueous systems using chemical analysis (a combination method) or not (an optimized sections method) to determine the composition of an equilibrium liquid phase.     

Post-Assembly Photomasking of Potassium Acyltrifluoroborates (KATs) for Two-Photon 3D Patterning of PEG-Hydrogels

Chemical ligation reactions of functional groups that can be masked with two-photon labile protecting groups provide a powerful technology for the three-dimensional patterning of molecules – including proteins – onto hydrogel scaffolds. In order to utilize readily prepared hydrogels constructed by the potassium acyltrifluoroborate (KAT)-hydroxylamine amide formation ligation for two-photon patterning, we have developed a unique post-polymerization protecting group strategy through the reaction of KATs and dithiols in water and deprotection by two-photon excitation. After precise 3D spatially confined light irradiation, the unprotected KATs undergo ligations with hydroxylamine-functionalized superfolder GFP and sulforhodamine B for the composition of three-dimensional patterns.     

Acid-catalyzed rearrangement of 3-(β-2-aminostyryl)quinoxalin-2(1H)ones—a new and efficient method for the synthesis of 2-benzimidazol-2-ylquinolines

A highly efficient, one-step, versatile method for the synthesis of 2-benzimidazol-2-ylquinolines has been developed on the basis of an acid-catalyzed rearrangement proceeding via a novel ring contraction of 3-(β-2-aminostyryl)quinoxalin-2(1H)ones.     

First study of rhodium(I) complexes with chiral sulfur-containing terpenoids as catalytic systems for ketone hydrosilylation

Abstract

Using a “chiral pool” approach, a number of chiral thiolate and sulfide ligands based on natural terpenes and terpenoids have been synthesized in a few simple steps. Two new Rh-thiolate complexes with the formula [Rh(CO)₂(μ-SR)]₂ were obtained. The influence of these complexes and catalytic systems formed by combining the synthesized ligands with [Rh(CO)₂(μ-Cl)]₂ and [Rh(cod)(μ-Cl)]₂, on the reaction rate, chemoselectivity, stereoselectivity and formation of tetraphenyldisiloxane in Rh-catalyzed asymmetric hydrosilylation of acetophenone as a model reaction have been studied. Mechanistic aspects of formation of silyl enol ether as a side product in the presence of S-containing ligands are presented.     

Salt solubility in the system KHCO3-(C2H5)2NH2Cl-H2O at 30°C

Salt solubility in the ternary system KHCO₃-(C₂H₅)₂NH₂Cl-H₂O was determined. This system is the diagonal cross-section of the quaternary mutual system K⁺,(C₂H₅)₂NH₂⁺∥HOO₃⁻, Cl⁻-H₂O along the stable pair of salts. The run of the saturation lines for the individual salts KHCO₃ and (C₂H₅)₂NH₂Cl was analyzed. This system was found to contain foreign phases and thus can be regarded as transient.     

Tackling the chemical diversity of microbial nonulosonic acids – a universal large-scale survey approach

Nonulosonic acids, commonly referred to as sialic acids, are a highly important group of nine-carbon sugars common to all domains of life. They all share biosynthetic and structural features, but otherwise display a remarkable chemical diversity. In humans, sialic acids cover all cells which makes them important for processes such as cellular protection, immunity and brain development. On the other hand, sialic acids and other nonulosonic acids have been associated with pathological processes including cancer and viral infections. In prokaryotes, nonulosonic acids are commonly associated with pathogens, which developed through molecular mimicry a strategy to circumvent the host''s immune response. However, the remarkably large chemical diversity of prokaryotic nonulosonic acids challenges their discovery, and research on molecular characteristics essential for medical applications are often not feasible. Here, we demonstrate a novel, universal large-scale discovery approach that tackles the unmapped diversity of prokaryotic nonulosonic acids. Thereby, we utilize selective chemical labelling combined with a newly established mass spectrometric all-ion-reaction scanning approach to identify nonulosonic acids and other ulosonic acid-like sugars. In doing so, we provide a first molecular-level comparative study on the frequency and diversity across different phyla. We not only illustrate their surprisingly wide-spread occurrence in non-pathogenic species, but also provide evidence of potential higher carbon variants. Many biomedical studies rely on synthetic routes for sialic acids, which are highly demanding and often of low product yields. Our approach enables large-scale exploration for alternative sources of these highly important compounds.

A novel large-scale survey approach for microbial nonulosonic acids (sialic acids) including a first molecular level comparative study is presented.     

A combined method for investigating solubility and determining the composition of equilibrium solid phases saturating eutonic solutions in a NaCl-Na2SO4-Na2CO3-H2O system at 50°C

The composition of equilibrium solid phases NaCl, Na₂SO₄, Na₂CO₃ · 2Na₂SO₄ (berkeyite) and NaCl, Na₂CO₃ · H₂O, Na₂CO₃ · 2Na₂SO₄ (without preparative determination), saturating E₁ and E₂ eutonic solutions respectively, was established via nonvariant area boundary determination in a NaCl-N₂SO₄- Na₂CO₃-H₂O system at 50°C with the use of a combined method.     

Topological Analysis of Electron Densities: Is the Presence of an Atomic Interaction Line in an Equilibrium Geometry a Sufficient Condition for the Existence of a Chemical Bond?

The structure, energetics, and electron density in the inclusion complex of He in adamantane, C10H16, have been studied by density functional theory calculations at the B3LYP6-311++G(2p,2d) level. Topological analysis of the electron density shows that the He atom is connected to the four tertiary tC atoms in the cage by atomic interaction lines with (3,-1) critical points. The calculated dissociation energy of the complex He@adamantane(g)=adamantane(g) + He(g) of DeltaE=-645 kJ mol(-1) nevertheless shows that the He-tC interactions are antibonding.