Radical Stabilization of a Tripyridinium-Triazine Molecule Enables Reversible Storage of Multiple Electrons.

A novel organic molecule, 2,4,6-tris[1-(trimethylamonium)propyl-4-pyridiniumyl]-1,3,5-triazine hexachloride, was developed as a reversible six-electron storage electrolyte for use in an aqueous redox flow battery (ARFB). Physicochemical characterization reveals that the molecule evolves from a radical to a biradical and finally to a quinoid structure upon accepting four electrons. Both the diffusion coefficient and the rate constant were sufficiently high to run a flow battery with low concentration and kinetics polarization losses. In a demonstration unit, the assembled flow battery affords a high specific capacity of 33.0 Ah L-1 and a peak power density of 273 mW cm-2 . This work highlights the rational design of electroactive organics that can manipulate multi-electron transfer in a reversible way, which will pave the way to development of energy-dense, manageable and low-cost ARFBs.

Brusatol.

The title compound, C(26)H(32)O(11), is composed of an α,ß-unsaturated cyclo-hexa-none ring (A), two cyclo-hexane rings (B and C), a six-membered lactone ring (D) and tetra-hydro-furan ring (E). Ring A exists in a half-chair conformation with a C atom displaced by 0.679 (2) Šfrom the mean plane through the remaining five atoms. Ring B exists in a normal chair conformation. Both rings C and D exist in a twisted-chair conformation due to the O-atom bridge and the carbonyl group in rings C and D, respectively. Ring E shows an envelope conformation with a C atom displaced by 0.761 (1) Šfrom the mean plane through the remaining five atoms. The ring junctions are A/B trans, B/C trans, C/D cis and D/E cis. An intra-molecular O-H⋯O hydrogen bond occurs. In the crystal, O-H⋯O hydrogen bonds involving the hy-droxy, lactone and ester groups and C-H⋯O inter-actions are observed.

14,15-Didehydro-hellebrigenin.

The title compound, C(24)H(30)O(5), is the didehydro product of the steroid hellebrigenin (systematic name: 3ß,5,14-trihy-droxy-19-oxo-5ß-bufa-20,22-dienolide). It consists of three cyclo-hexane rings (A, B and C), a five-membered ring (D) and a six-membered lactone ring (E). The stereochemistry of the ring junctions are A/B cis, B/C trans and C/D cis. Cyclo-hexane rings A, B and C have normal chair conformations. The five-membered ring D with the C=C bond adopts an envelope conformation. Lactone ring E is essentially planar with a mean derivation of 0.006 (4) Šand is ß-oriented at the C atom of ring D to which it is attached. There is an O-H⋯O hydrogen bond in the mol-ecule involving the hy-droxy groups. In the crystal, O-H⋯O hydrogen bonds link the mol-ecules into chains propagating along [010]. The chains are linked by C-H⋯O contacts into a three-dimensional network.

Phenylene-Bridged Bispyridinium with High Capacity and Stability for Aqueous Flow Batteries.

A rotating phenyl ring is introduced between the two pyridinium rings, namely, 1,1'-bis[3-(trimethylamonium)propyl]-4,4'-(1,4-phenylene)bispyridinium tetrachloride ((APBPy)Cl4 ), to form a switchable conjugation. In this design, the conjugation is switched "off" in the oxidized state and the two pyridinium rings behave independently during the redox process, yielding a concomitant transfer of two electrons at the same potential and, thus, simplifying the battery management. The conjugation is switched "on" in the reduced state and the charge can be effectively delocalized, lowering the Lewis basicity and improving its chemical stability. By pairing 0.50 m (APBPy)Cl4 with a 2,2,6,6-tetramethylpiperidin-1-yl oxyl derivative as the positive electrolyte, a flow battery delivers a high standard cell voltage of 1.730 V and a high specific capacity of 20.0 Ah L-1 . The battery also shows an exceptionally high energy efficiency of 80.8% and a superior cycling stability at 80 mA cm-2 . This strategy proves itself a great success in engineering viologen as a two-electron storage mediator with high capacity and stability.

Efficient Ultraviolet Light Detector Based on a Crystalline Viologen-Based Metal-Organic Framework with Rapid Visible Color Change under Irradiation.

A convenient colorimetric molecular system constructed by the zinc viologen-carboxylate framework is developed for naked eye detection of instantaneous UV exposure levels. Only narrow-band absorption in UV regions and a unique interpenetrated structure of its colorless crystal enable the system to give a fast response toward UV irradiance with intensity as low as 0.001 mw/cm2.

Isolation, chemotaxonomic significance and cytotoxic effects of quassinoids from Brucea javanica.

A new quassinoid, bruceene A (1) along with seventeen known quassinoids (2-18) was isolated from the fruits of Brucea javanica. The structure of 1 was elucidated by extensive spectroscopic methods, and was further confirmed by single-crystal X-ray diffraction analysis. Isolation of similar quassinoids 1-3 as those in genus Ailanthus from genus Brucea, indicated the close chemotaxonomic relationship between these two genera, which further supported the phylogenetic study by DNA analysis. Compounds 5, 7, 10 and 12 with a 3-hydroxy-3-en-2-one moiety showed potent inhibitory activities against the MCF-7 and MDA-MB-231 cells with IC50 values in the ranges 0.063-0.182 µM and 0.081-0.238 µM, respectively; while glycosidation at 3-OH significantly decreased the cytotoxicity. It was also found that the most potent compound 7 induced apoptosis in MCF-7 cells via the intrinsic mitochondrial apoptotic pathway.