Anthracenoyl crown ethers and cryptands as fluorescent probes for solid-phase transitions of phosphatidylcholines: syntheses and phospholipid membrane studies

Abstract

Three structurally related crown compounds and cryptands have been synthesized that differ by the number and linkage of coronand units and anthracene moieties. The interaction of the fluorescent dyes with sonicated dimyristoylphosphatidylcholine (DMPC) vesicles is characterized by the relative quantum yields, uptake kinetics, binding curves, lifetimes, fluorescence titrations with water- and lipid-soluble quenching agents, fluorescence anisotropy, and equilibrium cooling curves. The most lipophilic compound II, which displays a similar quantum yield as the parent fluorophore 9,10-dimethylanthracene, shows a nearly equal distribution between solid and fluid lipid and is located at the bilayer surface. The least lipophilic compound IV is excluded from the hydrocarbon phase. The anthracenophane cryptand III preferentially partitions into solid-phase lecithins with the highest affinity for the phases L epsilon and L beta. The binding constant to DMPC amounts to (5.4 +/- 1.3) X 10(2) M-1 at 0 degrees C. From fluorescence quenching titrations it is concluded that the average position of the anthracenoyl dye III discontinuously shifts during the gel to liquid crystalline transition from the glycerol backbone to the choline head group. Electron microscopy and NMR experiments revealed that the anthracenophane induces in the liquid crystalline phase the fusion of small unilamellar DMPC vesicles to unilamellar medium-sized vesicles and macrovesicles, which subsequently fuse at the transition temperature to large multilamellar coacervates. Due to its large change of fluorescence intensity, the anthracenophane cryptand is a very sensitive probe for the detection of the pretransition of symmetrically substituted and of the subtransition of asymmetrically substituted phosphatidylcholines.(ABSTRACT TRUNCATED AT 250 WORDS)

Crystallinity and Orientation Manipulation of Anthracene Diimide Polymers for All‐Polymer Solar Cells

“…Synthetic route of dibromide ADI monomer and two polymers is shown in Scheme 1. The tetrabromide anthracene 2 was prepared from starting material 1 according to the study by Herrmann et al, [48] which then followed acidation, acylation, and intramolecular Lewis acid-mediated double-cyclization reaction to yield the target monomer ADIOD-2Br (details shown in Supporting Information). [36,49,50] The dibromide monomer was then copolymerized with distannyl bithiophene and distannyl thiophene, respectively, to synthesize PADIOD-2T and PADIOD-T. Their molecular weights (M n ) and polydispersity index (PDI) determined by GPC are 14.2 kDa/2.3 and 32.7 kDa/4.5 (Table 1).…”

Anthracene‐Based Amido−Amine Cage Receptor for Anion Recognition under Neutral Aqueous Conditions

“…Moreover, the anthracene dye can provide fluorescence properties for a synthetic receptor. There have been only a few reports published on the use of derivatives of 1,8‐anthracene dicarboxylic acids in synthetic receptors, such as recognition of dicarboxylic acids and cations…”

“…Moreover, the anthracene dye can provide fluorescence properties for a synthetic receptor. There have been only a few reports published on the use of derivatives of 1,8-anthracene dicarboxylic acids in synthetic receptors, such as recognition of dicarboxylic acids [14] and cations [15] Herein, we report the design and synthesis of a new amidoÀ amine cage receptor, which combines in its structure 1,8-anthracene diacarboxamide subunit and a polyammonium azamacrocycle. The anthracene part serves not only as a source of hydrogen bond donor NH-groups and acceptor CO-groups, but also as a fluorescent dye for anion detection.…”

The oriented and patterned growth of fluorescent metal–organic frameworks onto functionalized surfaces

“…The synthesis of 9,10-anthracenedicarboxylic acid mainly followed the procedure described in the literature [55]. n -Butyllithium (22.5 mmol, 1.44 g) was added under nitrogen to a suspension of 9,10-dibromoanthracene (7.5 mmol, 2.50 g) in absolute diethyl ether (30 mL).…”