Inverted sapphyrin: a new family of doubly N-confused expanded porphyrins

The synthesis of an inverted, methoxylated sapphyrin derivative is described. This system, wherein inversion of pyrrolic nitrogen atoms is configurationally enforced via the use of a 3,3'-bipyrrolic precursor, displays what is best described as "weak aromaticity" as judged from its spectroscopic features and supporting theoretical calculations.     

New polyethyleneglycol-functionalized texaphyrins: synthesis and in vitro biological studies

The synthesis of four new analogues of motexafin gadolinium (MGd), a gadolinium(III) texaphyrin complex in clinical trials for its anticancer properties, is described. These new derivatives contain either 1,2-diaminobenzene or 2,3-diaminonaphthalene subunits as the source of the imine nitrogens and bear multiple 2-[2-(2-methoxyethoxy)ethoxy]ethoxy (PEG) groups, on either meso aryl or beta-pyrrolic substituents, to increase their water solubility. All four analogues were found to be more active in vitro than the parent system MGd as judged from cell proliferation assays using the PC3 and A549 cell lines.     

Immobilization of a hexaphyrin(1.0.1.0.0.0) derivative onto a tentagel-amino resin and its use in uranyl cation detection

The synthesis of an isoamethyrin derivative containing two CH(2)CH(2)CO(2)CH(3) moieties in the beta-pyrrolic positions and its use in the colorimetric detection of the uranyl cation after immobilization onto a solid support is reported.     

Dioxabenzosapphyrin: a new benzodifuran-derived sapphyrin analogue

The synthesis and characterization of a new sapphyrin analogue, dioxabenzosapphyrin, are reported. The benzodifuran moiety upon which this system is based leads to the incorporation of two oxygen atoms within the central macrocyclic core, thus replacing two protonated nitrogen centers found in normal pentaaza sapphyrin derivatives, including those derived from benzodipyrroles. As expected, the loss of these two NH hydrogen bond donor sites greatly reduces the anion affinity for the diprotonated form, even though the overall charge is the same as in the corresponding sapphyrins. Interestingly, dioxabenzosapphyrin, but not the corresponding all-aza systems, is found to bind neutral guests, such as phenol and 4-nitrophenol, albeit weakly. This latter finding highlights a potentially new application for core-modified expanded porphyrin derivatives, namely, as receptors for hydrogen bond donating neutral substrates.     

Trapping of Stable [4n+1] π-Electron Species from Peripherally Substituted,Conformationally Rigid,Antiaromatic Hexaphyrins

Peripherally substituted antiaromatic naphthorosarins have been synthesized for the first time. The synthesis was accomplished by acid-catalyzed condensation of naphthobipyrrole building blocks with aromatic aldehydes. The naphthobipyrrole building blocks were synthesized by simple oxidative coupling of the corresponding pyrrole substituted aromatics. Solid-state structural analyses of the synthesized naphthorosarins revealed that the presence of meso-2,6-dichlorophenyl- and 5,6-difluoro-substitution substantially alter the geometry and properties of the naphthorosarins. The substituents affect the redox potentials as well and, in turn, the proton-coupled electron-transfer processes leading to the formation of one- and two-electron reduced forms of the corresponding naphthorosarins. One particular naphthorosarin that bears both peripheral fluorine and meso-2,6-dichlorophenyl substituents forms a stable 25 π-electron species upon treating with TFA that was characterized by single-crystal X-ray diffraction analysis. The current study underscores how structural modifications can be used to fine-tune the electronic features of naphthorosarins, including stabilization of odd electron species.     

Morphology and electret behaviour of microcellular high glass temperature films

Here we report the processing of cellular, high-temperature polymers for electret applications based on polyetherimide (PEI) and polyetheretherketone (PEEK). The two approaches were utilized to improve the electret properties by insertion of cavities are the physical batch foaming process using carbon dioxide as the blowing agent and the stretching of polymeric plates containing suitable particles, which allows the manufacturing of porous films. The electret properties of foamed PEI and PEEK as well as stretched PEI containing NA11 particles are characterized by isothermal charge decay measurements at 90 °C after corona charging to surface potentials of about 400 V. Investigation of the cellular morphologies was achieved by scanning electron microscopy (SEM) and micro-computertomography (μCT). As result, the cellular films show a clear improved charge storage behaviour compared to the compact films. The best results were achieved with porous PEI films, prepared by stretching and after twofold charging. PACS 77.22.-d; 77.84.Jd; 73.61.Ph; 61.43.Gt; 52.80.Hc     

Stacked and folded piezoelectrets for vibration-based energy harvesting

ABSTRACT

Vibration-based energy harvesting with piezoelectrets can be significantly improved by using multiple layers of these materials. In particular, folding or stacking of piezoelectrets or a combination of these methods results in increased power output of the energy harvesters. The possibilities of these procedures are explored, together with the effect of seismic mass, resonance frequency, and terminating resistance. It is found that with seismic masses of about 20 g and using radiation-crosslinked polypropylene (IXPP) as a piezoelectret, power outputs of up to 80 µW can be achieved for an acceleration of 1 g. Expected dependencies of generated power on frequency, folding and stacking parameters, in particular number of layers, and on seismic mass, are confirmed.     

Electron-transfer and acid-base properties of a two-electron oxidized form of quaterpyrrole that acts as both an electron donor and an acceptor

Electron-transfer interconversion between the four-electron oxidized form of a quaterpyrrole (abbreviated as P4 for four pyrroles) and the two-electron oxidized form (P4H2) as well as between P4H2 and its fully reduced form (P4H4) bearing analogous substituents in the alpha- and beta-pyrrolic positions was studied by means of cyclic voltammetry and UV-visible spectroelectrochemistry combined with ESR and laser flash photolysis measurements. The two-electron oxidized form, P4H2, acts as both an electron donor and an electron acceptor. The radical cation (P4H2*+) and radical anion (P4H2*-) are both produced by photoinduced electron transfer from dimeric 1-benzyl-1,4-dihydronicotinamide to P4H2, whereas the cation radical form of the compound is also produced by electron-transfer oxidation of P4H2 with [Ru(bpy)3]3+. The ESR spectra of P4H2*+ and P4H2*- were recorded at low temperature and exhibit spin delocalization over all four pyrrole units. Thus, the two-electron oxidized form of the quaterpyrrole (P4H2) displays redox and electronic features analogous to those seen in the case of porphyrins and may be considered as a simple, open-chain model of this well-studied tetrapyrrolic macrocycle. The dynamics of deprotonation from P4H2*+ and disproportionation of P4H2 were examined by laser flash photolysis measurements of photoinduced electron-transfer oxidation and reduction of P4H2, respectively.