Supermolecular control of charge transfer in dye-sensitized nanocrystalline TiO2 films: towards a quantitative structure-function relationship.
Tigliane diterpenes from the latex of Euphorbia obtusifolia with inhibitory activity on the mammalian mitochondrial respiratory chain
Abstract Six diterpenes isolated from the latex of Euphorbia obtusifolia Poir. (Euphorbiaceae) were evaluated for their inhibition of the NADH oxidase activity in submitochondrial particles from beef heart. 4,20-Dideoxyphorbol-12,13-bis(isobutyrate) was the most potent inhibitor and showed an inhibitory concentration with IC 50 value of 2.6±0.3 mM. In the present study, some structure–activity trends are suggested for the inhibitory activity of the mammalian mitochondrial respiratory chain of these natural product derivatives of 4-deoxyphorbol esters.
Optical sensing of cyanide using hybrid biomolecular films
The selective sensing of cyanide anions in water has been studied using a hybrid biomaterial composed of a mesoporous TiO2 film of crystalline nanoparticles and the protein hemoglobin. The mesoporous structure of the film prevents protein unfolding and also stabilizes the oxidized form of the prosthetic groups. Low-levels of cyanide anions (<0.2 ppm (0.2 mgr/L)) can be detected by monitoring the changes in the optical properties of the hybrid biomolecular films upon cyanide binding to the heme groups.
Dynamic chemical devices: photoinduced electron transfer and its ion-triggered switching in nanomechanical butterfly-type bis(porphyrin)terpyridines.
A series of butterfly-type molecular constructs has been prepared in good yield by using a double Stille coupling synthetic protocol. They are composed of a terpyridine (terpy) scaffold and two wings composed of appended porphyrins that are capable of switching from an extended W geometry to a compact U geometry upon cation coordination of the terpy unit. The porphyrin moieties exist in the constructs either as free bases or they can be sequentially metallated, thus giving rise to wings of different "colours". Stationary and time-resolved emission studies of the HZn, ZnAu and Zn2Au constructs show that the electronic properties are strongly dependent on the geometry. In the extended W confo…
Reversible Colorimetric Probes for Mercury Sensing
The selectivity and sensitivity of two colorimetric sensors based on the ruthenium complexes N719 [bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) bis(tetrabutylammonium) bis(thiocyanate)] and N749 [(2,2':6',2' '-terpyridine-4,4',4' '-tricarboxylate)ruthenium(II) tris(tetrabutylammonium) tris(isothiocyanate)] are described. It was found that mercury ions coordinate reversibly to the sulfur atom of the dyes' NCS groups. This interaction induces a color change in the dyes at submicromolar concentrations of mercury. Furthermore, the color change of these dyes is selective for mercury(II) when compared with other ions such as lead(II), cadmium(II), zinc(II), or iron(II). The detection limit…
State selective electron injection in non-aggregated titanium phthalocyanine sensitised nanocrystalline TiO2 films
We describe a novel titanium phthalocyanine that shows no aggregation when anchored to nanocrystalline TiO2 films through its axial carboxylated ligand without the use of co-adsorbents; state selective electron injection into the TiO2 is demonstrated, resulting in efficient photocurrent generation in dye sensitised photoelectrochemical solar cells. Palomares Gil, Emilio J, epagil@alumni.uv.es
Jatrophane and tigliane diterpenes from the latex of Euphorbia obtusifolia
The latex of Euphorbia obtusifolia var. obtusifolia yielded twelve new diterpene polyesters. Seven of them displayed the jatrophane framework and five were 4-deoxyphorbol esters. A further isolated tigliane diterpene, a derivative of 4-epi-4-deoxyphorbol, was most likely an artifact of the isolation procedure. All structures were established with the aid of spectroscopic methods.
Solid film versus solution-phase charge-recombination dynamics of exTTF-bridge-C60 dyads.
The charge-recombination dynamics of two exTTF-C 6 0 dyads (exTTF=9,10-bis(l,3-dithiol-2-ylidene)-9,10-dihydroanthracene), observed after photoinduced charge separation, are compared in solution and in the solid state. The dyads differ only in the degree of conjugation of the bridge between the donor (exTTF) and the acceptor (C 6 0 ) moieties. In solution, photoexcitation of the nonconjugated dyad C 6 0 -BN-exTTF (1) (BN=1,1'-binaphthyl) shows slower charge-recombination dynamics compared with the conjugated dyad C 6 0 -TVB-exTTF (2) (TVB = bisthienylvinylenebenzene) (lifetimes of 24 and 0.6 μs, respectively), consistent with the expected stronger electronic coupling in the conjugated dyad.…
Acid versus base peptization of mesoporous nanocrystalline TiO2 films: functional studies in dye sensitized solar cells
We report an analysis of the influence of acid/base conditions employed in the synthesis of TiO2 nanoparticles upon the performance of dye sensitised photoelectrochemical solar cells fabricated from these particles. The functional properties of the TiO2 nanoparticles in these devices are investigated by potential step chronoamperometry, transient laser spectroscopy, and photovoltaic device characterisation. We find that base peptization conditions employed in the sol–gel fabrication of the TiO2 nanoparticles result in a reduction in film electron density under negative applied bias, correlated with slower interfacial recombination losses and a higher device open circuit voltage.
Cover Picture: Dynamic Chemical Devices: Photoinduced Electron Transfer and Its Ion-Triggered Switching in Nanomechanical Butterfly-Type Bis(porphyrin)terpyridines (Chem. Eur. J. 7/2006)
Optical mercury sensing using a benzothiazolium hemicyanine dye.
[structure: see text] The selectivity and sensitivity of a benzothiazolium hemicyanine dye toward mercury(II) in aqueous solutions are described. Mercury ions coordinate to the dye forming a 1:1 complex. This interaction induces a color change in the dye at micromolar concentrations of mercury. Furthermore, the color change and quenching of the dye emission are selective for mercury when compared with other ions such as lead(II), cadmium(II), zinc(II), or iron(II).
Hybrid molecular materials for optoelectronic devices
Hybrid molecular materials based on semiconductor nanocrystalline metal oxides are a subject of intense research for the development of optoelectronic devices. Such devices follow the strategy of combining high surface area mesoporous materials with optically and electrochemically active molecules. Photovoltaic devices, molecular sensors and biosensors are some of the examples discussed in this paper.
The origin of slow electron recombination processes in dye-sensitized solar cells with alumina barrier coatings
We investigate the effect of a thin alumina coating of nanocrystalline TiO2 films on recombination dynamics of dye-sensitized solar cells. Both coated and uncoated cells were measured by a combination of techniques: transient absorption spectroscopy, electrochemical impedance spectroscopy, and open-circuit voltage decay. It is found that the alumina barrier reduces the recombination of photoinjected electrons to both dye cations and the oxidized redox couple. It is proposed that this observed retardation can be attributed primarily to two effects: almost complete passivation of surface trap states in TiO2 that are able to inject electrons to acceptor species, and slowing down by a factor of…
Determination of electron and hole energy levels in mesoporous nanocrystalline TiO2 solid-state dye solar cell
A study of a hybrid heterojunction solar cell based on nanocrystalline mesoporous TiO2 and the hole conductor spiro-OMeTAD (2,2′7,7′-tetrakis(N,N′-di-p-methoxyphenyl-amine)-9,9′-spiro-bifluorene) has been realized. Impedance and cyclic voltammetry techniques were used to measure the interfacial properties of the hybrid heterojunction and establish the energy levels of the solid-state electrolyte. It was observed that the energy levels of the organic hole transport material are changed when it forms a film deposited onto indium-doped tin oxide (ITO). Moreover, the HOMO level of the mono oxidized spiro-OMeTAD is well coupled with the HOMO level of the dye N719 (Ru(4,4′-dicarboxy-2,2′-bipyridy…
A Highly Sensitive Hybrid Colorimetric and Fluorometric Molecular Probe for Cyanide Sensing Based on a Subphthalocyanine Dye
A highly sensitive, selective colorimetric and fluorometric molecular probe based on a subphthalocyanine dye has been developed for cyanide-anion determination in aqueous solution. It has also been shown that a carboxysubphthalocyanine derivative can be covalently anchored to transparent mesoporous nanocrystalline high-surface-area metal oxide films to detect low concentrations of cyanide anion in pure water with no interference from other anionic or cationic species.