Competition between photodimerization and photocycloaddition of dimethyl 3-dehydrogibberellenate to ethylene, 1,1-dichloroethylene and trichloroethylene

Photocycloadditions of dimethyl 3-dehydrogibberellenate 1 to ethylene, 1,1-dichloroethylene and trich-loro-ethylene were investigated The results exhibited markedly the competition between photodimerization and photocycloaddition of 1, and showed that the yields of cycloaddition products increased with increasing polarity of the olefins. Strangely, photocycloaddition of 1 to olefins was found to proceed through the singlet excited state     

Diversity-oriented synthesis of biaryl-containing medium rings using a one bead/one stock solution platform

Diversity-oriented synthesis of structurally complex and diverse small molecules can be used as the first step in a process to explore cellular and organismal pathways. The success of this process is likely going to be dependent on advances in the synthesis of small molecules having natural product-like structures in an efficient and stereoselective manner. The development, scope, and mechanism of the oxidation of organocuprates was investigated and exploited in the atropdiastereoselective synthesis of biaryl-containing medium rings (9-, 10-, and 11-membered rings). The methodology was performed on high-capacity, large polystyrene beads by metalating aryl bromides with i-PrBu(2)MgLi, followed by transmetalating with CuCN x 2LiBr and then oxidizing with 1,3-dinitrobenzene, and was used in a diversity-oriented synthesis of biaryl-containing medium rings (library total theoretical maximum 1412 members). The high capacity beads were arrayed into 384-well plates and, using a process optimized during the development of a one bead/one stock solution technology platform, converted into arrays of stock solutions, with each stock solution containing largely one compound. These stock solutions were used in numerous phenotypic and protein-binding assays. The process described outlines a pathway that we feel will contribute to a comprehensive and systematic chemical approach to exploring biology (chemical genetics).     

Development of a multi-target screening analysis for 301 drugs using a QTrap liquid chromatography/tandem mass spectrometry system and automated library searching

A new multi-target screening (MTS) procedure for drugs in blood and urine for toxicological analysis has been developed using a hybrid triple-quadrupole linear ion trap mass spectrometer (QTrap) for the fast detection and identification of 301 forensically important drugs, e.g. tranquilizers (benzodiazepines), hypnotics, drugs of abuse (opiates, cocaine, amphetamines, cannabinoids), antidepressants, neuroleptics, and some cardiac drugs, in one single liquid chromatography/tandem mass spectrometry (LC/MS/MS) analysis. Samples were extracted either with liquid-liquid extraction or solid-phase extraction. A multiple reaction monitoring (MRM) as survey scan and an enhanced product ion (EPI) scan as dependent scan were performed in an information-dependent acquisition (IDA) experiment. Finally, drug identification was carried out by library search with a newly developed MS/MS library based on EPI spectra at three different collision energies in positive mode. The advantage of this newly developed method is the possibility to detect and identify 301 drugs in one single LC/MS/MS run.     

Comparative structural characterization of the water dispersions of detonation nanodiamonds by small-angle neutron scattering

The structure of nanodiamond water dispersions prepared under different conditions was investigated by small-angle neutron scattering at the scale of 1 to 100 nm. The study of diluted dispersions was regarded as of paramount importance. Similarly to previous studies, strong clustering of particles was revealed in the solutions. The typical size of clusters (40 nm and above) depends on the modification of the dispersions. A common property can be distinguished for different systems: the fractal dimension of the clusters is in the range of 2.3?C2.4, which indicates that there is a common clustering mechanism in such systems. Using contrast variation, the existence of a nondiamond component in the colloidal particles of the dispersions was confirmed; it correlates with the presence of a graphene shell on crystallite surfaces.     

Polymer Composites with Plasma-Treated Fillers

A Large-volume Microwave Plasma (LMP) generator has been used to irradiate mica and ground-wood fibers in inert and active gas environments. Irradiated fillers were subsequently incorporated in a polypropylene matrix at solids levels of 10 and 20%. Calorimetrically measured heats of immersion showed that substantial changes in surface properties of fillers were effected by irradiation in ethylene, ammonia, and similar active gases. These surface changes are reflected In ultimate tensile and elongation properties of composites which show marked improvement over controls based on unirradiated fillers. Although no appreciable response in melt viscosity has been observed, surface treatment of fillers does seem to increase significantly melt elasticity of filled composites. The implications of improved performance motivate a more detailed study of the use potential of LMP in the fomulation of polymer composites.     

Multivalent ions and biomolecules: Attempting a comprehensive perspective

Ions are ubiquitous in nature. They play a key role for many biological processes on the molecular scale, from molecular interactions, to mechanical properties, to folding, to self-organisation and assembly, to reaction equilibria, to signalling, to energy and material transport, to recognition etc. Going beyond monovalent ions to multivalent ions, the effects of the ions are frequently not only stronger (due to the obviously higher charge), but qualitatively different. A typical example is the process of binding of multivalent ions, such as Ca²⁺, to a macromolecule and the consequences of this ion binding such as compaction, collapse, potential charge inversion and precipitation of the macromolecule. Here we review these effects and phenomena induced by multivalent ions for biological (macro)molecules, from the “atomistic/molecular” local picture of (potentially specific) interactions to the more global picture of phase behaviour including, e. g., crystallisation, phase separation, oligomerisation etc. Rather than attempting an encyclopedic list of systems, we rather aim for an embracing discussion using typical case studies. We try to cover predominantly three main classes: proteins, nucleic acids, and amphiphilic molecules including interface effects. We do not cover in detail, but make some comparisons to, ion channels, colloidal systems, and synthetic polymers. While there are obvious differences in the behaviour of, and the relevance of multivalent ions for, the three main classes of systems, we also point out analogies. Our attempt of a comprehensive discussion is guided by the idea that there are not only important differences and specific phenomena with regard to the effects of multivalent ions on the main systems, but also important similarities. We hope to bridge physico-chemical mechanisms, concepts of soft matter, and biological observations and connect the different communities further.     

Sterically Shielded Heptamethine Cyanine Dyes for Bioconjugation and High Performance Near‐Infrared Fluorescence Imaging

The near‐infrared window of fluorescent heptamethine cyanine dyes greatly facilitates biological imaging because there is deep penetration of the light and negligible background fluorescence. However, dye instability, aggregation, and poor pharmacokinetics are current drawbacks that limit performance and the scope of possible applications. All these limitations are simultaneously overcome with a new molecular design strategy that produces a charge balanced and sterically shielded fluorochrome. The key design feature is a meso‐aryl group that simultaneously projects two shielding arms directly over each face of a linear heptamethine polyene. Cell and mouse imaging experiments compared a shielded heptamethine cyanine dye (and several peptide and antibody bioconjugates) to benchmark heptamethine dyes and found that the shielded systems possess an unsurpassed combination of photophysical, physiochemical, and biodistribution properties that greatly enhance bioimaging performance.     

Investigation of the deformed region on the (111) plane of MgO crystals by cathodoluminescence method

The (111) plane of MgO single crystals was deformed by a concentrated load. It was observed that the number of rows of a cathodoluminescence rosette is a factor of two lower than that for the etch pit one. The explanation of this phenomenon is given. The polarity of plastic deformation was revealed using both an etch pit technique and cathodoluminescence method. It is shown that deformation causes a change of the cathodoluminescence spectra. The spectra, obtained from crystal deformed by indentation and from compressed crystal, are similar.