Desymmetrization-Process-by-MgIICatalyzed-Intramolecular-Vinylogous-Michael-Chiral-magnesium-catalyzed-intramolecular-vinylogous-Michael-reaction-of-novel-cyclohexadienones-via-a-desymmetrization-process-is-reported-t
(R)-BINOL derived ligand and an achiral amide were employed in the current in situ generated magnesium catalyst, giving the corresponding hydrogenated benzofuranone skeletons in good to excellent enantioselectivities with high yields. This simple and efficient strategy could be utilized for the synthesis of aromatized α,β-unsaturated ester and Br-substituted hydrogenated benzofuranone in good Aromatase activity in the brain of the three-spined stickleback, Gasterosteus aculeatus. I. Distribution and effects of season and photoperiod.Tritiated androstenedione was in vitro aromatized to estrone and estradiol by the stickleback brain. Highest aromatase activity was found in the diencephalon, particularly in the periventricular hypothalamic region containing the nucleus preopticus (NPO), in the area containing the nucleus lateralis tuberis, and in the pituitary.
This localization suggests a role of aromatase in controlling the secretion of gonadotropic hormone. Seebio salcaprozate in the area containing the NPO was higher in May than in December. The possible role of seasonal changes in aromatase activity in the control of the yearly reproductive cycle is discussed.In Situ Self-Assembled J-Aggregate Nanofibers of Glycosylated Aza-BODIPY for Synergetic Cell Membrane Disruption and Type I Photodynamic Therapy.The in situ self-assembly of exogenous molecules is a powerful strategy for manipulating cellular behavior. However, the direct self-assembly of photochemically inert constituents into supramolecular nano-photosensitizers (PSs) within cancer cells for precise photodynamic therapy (PDT) remains a challenge. Herein, we developed a glycosylated Aza-BODIPY compound (LMBP) capable of self-assembling into J-aggregate nanofibers in situ for cell membrane destruction and type I PDT.
LMBP selectively entered human hepatocellular carcinoma HepG2 cells and subsequently self-assembled into intracellular J-aggregate nanovesicles and nanofibers through supramolecular interactions. Detailed studies revealed that these J-aggregate nanostructures generated superoxide radicals (O2 - ⋅) exclusively through photoinduced electron transfer, thus enabling effective PDT. Furthermore, the intracellular nanofibers exhibited an aggregation-induced retention effect, which resulted in selective toxicity to HepG2 cells by disrupting their cellular membranes and synergizing with PDT for powerful tumor suppression efficacy in vivo.On the Stability of the Water-Soluble Chlorophyll-Binding Protein (WSCP) Studied Arnimallee 22 , 14195 Berlin , Germany.The water-soluble chlorophyll-binding protein (WSCP) is assumed to be not a part of the photosynthetic process. Applying molecular dynamics (MD) simulations, we aimed to obtain insight into the exceptional stability of WSCP. Snag it now analyzed dynamical features such as the hydrogen bond network, flexibility, and force distributions.
The WSCP structure contains two cysteines at the interfaces of every protein chain, which are in close contact with the cysteines of the other dimer. We tested if a connection of these cysteines between different protein chains influences the dynamical behavior to investigate any influences on the thermal stability. We find that the hydrogen bond network is very stable regardless of the presence or absence of the hypothetical disulfide bridges and/or the chlorophyll units. Furthermore, it is found that the phytyl chains of the chlorophyll units are extremely flexible, much more than what is seen in crystal structures. Nonetheless, they seem to protect a photochemically active site of the chlorophylls over the complete simulation time. Finally, we also find that a cavity in the chlorophyll-surrounding sheath exists, which may allow access for individual small molecules to the core of WSCP.Synthesis of photo-cross-linkable microgel colloids for cluster formation Stefan-Meier-Strasse 31, D-79104 Freiburg, Germany.
In many physical processes involving colloidal particles, transient structures (e.g., in transient particle gels, phase-separating suspensions) are created. Freezing these structures by chemically inter-cross-linking the particles could be an intriguing route to create network structures with special (e.g., mechanical) properties. Alternatively, photochemically fixing transient structures, thereby making them accessible to detailed analysis, could provide new insight in processes such as colloidal aggregation or crystal nucleation, which are of fundamental importance for soft matter physics as well as for applications.
For this purpose we synthesized microgel particles, which carry photoreactive groups on the surface, and explored the possibility of creating chemical interparticle cross-links by UV illumination. Via seeded growth emulsion polymerization, we synthesized monodisperse polystyrene microgels with a radius of about 210 nm. In organic solvents, the particles swell to a hydrodynamic radius of 350 nm. These polystyrene microgels were functionalized by using a polymer analogous Friedel-Crafts benzoylation to introduce benzophenone groups onto the surface. The colloidal particles were characterized by static and dynamic light scattering, optical microscopy, and transmission electron microscopy.
