Synthesis of Meso‐Substituted Subphthalocyanine–Subporphyrin Hybrids: Boron Subtribenzodiazaporphyrins

The first syntheses of hybrid structures that lie between subphthalocyanines and subporphyrins are reported. The versatile single‐step synthetic method uses a preformed aminoisoindolene to provide the bridging methine unit and its substituent while trialkoxyborates simultaneously act as Lewis acid, template, and provider of the apical substituent. The selection of each component therefore allows for the controlled formation of diverse, differentially functionalized systems. The new hybrids are isolated as robust, pure materials that display intense absorption and emission in the mid‐visible region. The new compounds are further characterized in solution and solid state by variable‐temperature NMR spectroscopy and X‐ray crystallography, respectively.     

Optimisation of isolation procedure for pyrrolizidine alkaloids from Rindera umbellata Bunge

Procedure for isolation of pyrrolizidine alkaloids (PAs) from Rindera umbellata Bunge plant species was optimised. Different extraction media (methanol, ethanol and sulphuric acid), concentration and volume of sulphuric acid, pH of PA solution for alkaline extraction, extraction time and techniques (maceration, ultrasonic and overhead rotary mixer assisted extraction) were investigated. The yields of six PAs (7-angeloyl heliotridane, 7-angeloyl heliotridine, lindelofine, 7-angeloyl rinderine, punctanecine and heliosupine) were monitored by GC–MS/FID. The best results for the isolation all of six PAs were obtained when the extraction was performed with 1 M sulphuric acid (30 mL per 1.00 g of dried sample) by overhead rotary mixer during three days. Optimal pH value for alkaline extraction of PAs with CH₂Cl₂ was 9, and the extraction should be performed with four portions of 30 mL of CH₂Cl₂. This procedure could be also useful for a plant sample preparation for GC and LC analyses of PAs.     

Using Laplacian Eigenvalues and Eigenvectors in the Analysis of Frequency Assignment Problems

A Frequency Assignment Problem (FAP) is the problem that arises when frequencies have to be assigned to a given set of transmitters so that spectrum is used efficiently and the interference between the transmitters is minimal. In this paper we see the frequency assignment problem as a generalised graph colouring problem, where transmitters are presented by vertices and interaction between two transmitters by a weighted edge. We generalise some properties of Laplacian matrices that hold for simple graphs. We investigate the use of Laplacian eigenvalues and eigenvectors as tools in the analysis of properties of a FAP and its generalised chromatic number (the so-called span).     

On the Nature of the Bonding in Coinage Metal Halides

This article analyzes the nature of the chemical bond in coinage metal halides using high-level ab initio Valence Bond (VB) theory. It is shown that these bonds display a large Charge-Shift Bonding character, which is traced back to the large Pauli pressure arising from the interaction between the bond pair with the filled semicore d shell of the metal. The gold-halide bonds turn out to be pure Charge-Shift Bonds (CSBs), while the copper halides are polar-covalent bonds and silver halides borderline cases. Among the different halogens, the largest CSB character is found for fluorine, which experiences the largest Pauli pressure from its σ lone pair. Additionally, all these bonds display a secondary but non-negligible π bonding character, which is also quantified in the VB calculations.     

Modification of the rheological properties of polyurethanes by adding fumed silica: influence of the preparation procedure

The way of addition of fumed silica determined the rheological properties of polyurethane (PU) adhesives. The higher the shear rate during preparation of fumed silica containingPU adhesives, the higher viscosity and improved plasticity and thixotropy in the solutions. The improved properties of these adhesive solutions were ascribed to the creation of interactions between the silanol groups on the fumed silica, the polar groups in the soft segments of the polyurethane and/or the solvent. However, the way of incorporate the fumed silica in the polyurethane did not affect the rheological properties of fumed silica-PU composites (obtained by solvent removal from the solutions), indicating the key role of the solvent in the rheology of PU adhesive solutions.     

The Influence of Chemical Change on Protein Dynamics: A Case Study with Pyruvate Formate-Lyase

Pyruvate formate-lyase (PFL) catalyzes the reversible conversion of pyruvate and coenzyme A (CoA) into formate and acetyl-CoA in two half-reactions. For the second half-reaction to take place, the S−H group of CoA must enter the active site of the enzyme to retrieve a protein-bound acetyl group. However, CoA is bound at the protein surface, whereas the active site is buried in the protein interior, some 20–30 Å away. The PFL system was therefore subjected to a series of extensive molecular dynamics simulations (in the μs range) and a host of advanced analysis procedures. Models representing PFL before and after the first half-reaction were used to examine the possible effect of enzyme acetylation. All simulated structures were found to be relatively stable compared to the initial crystal structure. Although the adenine portion of CoA remained predominantly bound at the protein surface, the binding of the S−H group was significantly more labile. A potential entry channel for CoA, which would allow the S−H group to reach the active site, was identified and characterized. The channel was found to be associated with accentuated fluctuations and a higher probability of being in an open state in acetylated systems. This result suggests that the acetylation of the enzyme assumes a prominent functional role, whereby the formation of the acyl intermediate serves to initiate a subtle signaling cascade that influences the protein dynamics and facilitates the entry of the second substrate.     

DNA binding and antitumor activities of zinc(II) complexes with some S-alkenyl derivatives of thiosalicylic acid

Transition Metal Chemistry - Two zinc(II) complexes with S-alkenyl derivatives of thiosalicylic acid as ligands have been synthesized and characterized by microanalysis, IR, 1H and 13C NMR...