One-pot synthesis of pyrrole-2-carboxylates and -carboxamides via an electrocyclization/oxidation sequence.

An electrocyclic ring closure is the key step of an efficient one-pot method for the synthesis of pyrrole-2-carboxylates and -carboxamides from chalcones and glycine esters or amides. The 3,4-dihydro-2H-pyrrole intermediates generated in situ are oxidized to the corresponding pyrroles by stoichiometric oxidants or by catalytic copper(II) and air in moderate to high yields. A wide range of functional groups are tolerated, and further combination with an in situ bromination gives access to polyfunctional pyrrole scaffolds.

Metallopolymer Organohydrogels with Photo-Controlled Coordination Crosslinks Work Properly Below 0 °C.

Controlling the structures and functions of gels is important for both fundamental research and technological applications. Introducing photoresponsive units into gels enables remote control of their properties with light. However, existing gels show photoresponsiveness only at room temperature or elevated temperatures. The development of photoresponsive gels that work below 0 °C can expand their usage in cold environments. Here, photoresponsive metallopolymer organohydrogels that function even at -20 °C are reported. The organohydrogels are prepared using photoresponsive Ru-thioether coordination bonds as reversible crosslinks to form polymer networks. A water/glycerol mixture is used as an anti-freezing solvent. At -20 °C, the Ru-thioether coordination bonds are dissociated under light irradiation and reformed reversibly in the dark, which result in alternating crosslinking densities in the polymer networks. This process enables inducing reversible gel-to-sol transitions, healing damaged gels, controlling the mechanical properties and volumes of the gels, and rewriting microstructures on the gels below 0 °C.

Nanostructured polymer assemblies stabilize photoactivatable anticancer ruthenium complexes under physiological conditions.

Photoactivatable ruthenium (Ru) complexes are promising compounds for anticancer phototherapy. They must be stable under physiological conditions before they are transported to cancer cells. In this paper, we systematically studied the stabilities of two Ru-containing block copolymers (Ru complexes as side group or in main chain, respectively) and their corresponding Ru complexes in different media, including saline, bovine serum albumin (BSA) solution, Dulbecco's Modified Eagle's Medium (DMEM, pH 6.5) and DMEM (pH 5.5) with 1.0 mM glutathione (GSH). Their stabilities were studied by monitoring the metal-to-ligand charge transfer (MLCT) bands of the Ru moieties via UV-Vis absorption spectroscopy. The MLCT bands of Ru complexes changed to varying degrees within a day in the above-mentioned media, indicating that they were instable. In contrast, the MLCT bands of Ru-containing polymer assemblies did not change significantly under the same conditions. These results showed that the self-assembled nanostructures protected the Ru moieties and improved their stability. In addition, these nanostructured polymer assemblies could be activated by red light. Therefore, the studied Ru-containing polymer assemblies are more suitable for in vivo applications than their low-molecular weight analogues.

Reconfiguring surface functions using visible-light-controlled metal-ligand coordination.

Most surfaces are either static or switchable only between "on" and "off" states for a specific application. It is a challenge to develop reconfigurable surfaces that can adapt to rapidly changing environments or applications. Here, we demonstrate fabrication of surfaces that can be reconfigured for user-defined functions using visible-light-controlled Ru-thioether coordination chemistry. We modify substrates with Ru complex Ru-H2O. To endow a Ru-H2O-modified substrate with a certain function, a functional thioether ligand is immobilized on the substrate via Ru-thioether coordination. To change the surface function, the immobilized thioether ligand is cleaved from the substrate by visible-light-induced ligand dissociation, and then another thioether ligand with a distinct function is immobilized on the substrate. Different thioethers endow the surface with different functions. Based on this strategy, we rewrite surface patterns, manipulate protein adsorption, and control surface wettability. This strategy enables the fabrication of reconfigurable surfaces with customizable functions on demand.

Structure-Function Evaluation of Imidazopyridine Derivatives Selective for δ-Subunit-Containing γ-Aminobutyric Acid Type A (GABAA) Receptors.

δ-Selective compounds 1 and 2 (DS1, compound 22; DS2, compound 16) were introduced as functionally selective modulators of δ-containing GABA type A receptors (GABAAR). In our hands, [3H]EBOB-binding experiments with recombinant GABAAR and compound 22 showed no proof of δ-selectivity, although there was a minimally higher preference for the α4ß3δ and α6ß2/3δ receptors with respect to potency. In order to delineate the structural determinants of δ preferences, we synthesized 25 derivatives of DS1 and DS2, and investigated their structure-activity relationships (SAR). Four of our derivatives showed selectivity for α6ß3δ receptors (29, 38, 39, and 41). For all of them, the major factors that distinguished them from compound 22 were variations at the para-positions of their benzamide groups. However, two compounds (29 and 39), when tested in the presence of GABA, revealed effects at several additional GABAAR. The newly synthesized compounds will still serve as useful tools to investigate α6ß3δ receptors.