RESUMEN

A clear case of relationship between the monomer molecular structure and the capability of tuning the morphology of electrodeposited gas bubbles template polymer thin films is shown. To this end, a series of fluorene-bridged dicarbazole derivatives containing either linear or terminally branched polyfluorinated side chains connected to the fluorene subunit were synthesized and their electrochemical properties were investigated. The new compounds underwent electrochemical polymerization over indium tin oxide electrodes to give hydrophobic films with nanostructural and morphological properties strongly dependent on the nature of the side chains. Gas bubbles templated electropolymerization was next achieved by the addition of tiny amounts of water to the monomer solutions, without using surfactants. Within the investigated set of molecules, the nanostructural properties of the soft-templated films obtained from monomers bearing linear side chains could be fine-tuned by adjusting electrochemical parameters, leading to superhydrophobic surfaces.

Asunto(s)

Nanoestructuras , Interacciones Hidrofóbicas e Hidrofílicas , Nanoestructuras/química , Agua , Fluorenos

RESUMEN

Lead sulfide (PbS) nanoparticles were synthesized by chemical methods with different sizes and different capping ligands (oleic acid, myristic acid, and hexanoic acid), avoiding ligand exchange procedures, to study the effect of characteristics of the capping ligands on their energy levels and band gap values. Experimental results (UV-vis-NIR, Fourier transform infrared, and Raman spectroscopies, cyclic voltammetry, transmission electron microscopy, and electron energy loss spectroscopy) showed a marked influence of the capping ligand nature on the electro-optical properties of PbS nanoparticles with a very similar size. Differences were observed in the atomistic arrangement on the nanoparticle surface and phonon vibrations with the different capping ligands. These observations suggest that the electro-optical properties of PbS nanoparticles are not only determined by their size, through quantum confinement effects, but also strongly affected by the atomistic arrangement on the nanoparticle surface, which is determined by the capping ligand nature.

RESUMEN

A new donor/acceptor (D-A) spiro dye (SCPDT1) featuring two bithiophene units, connected through an sp(3)-hybridized carbon atom, was prepared by a multistep synthetic sequence involving the convenient assembly of the spiro system under mild catalytic conditions. The photocurrent spectrum of dye-sensitized solar cells incorporating SCPDT1 covers the spectral region ranging from 350 to 700 nm and reaches a wide maximum of ~80% in the 420-560 nm range. Power conversion efficiencies of up to 6.02% were obtained.

RESUMEN

The particular properties of carbon nanoparticles (CNPs) have generated great interest in biomedicine, bioanalysis and optoelectronics. However, an association between the CNPs' physicochemical properties with their molecular and morphological characteristics is, even today, a topic of discussion. In this work, we use a simple method of synthesis with the ultimate aim of elucidating the structural nature of the obtained CNPs and its relationship with their well-known fluorescent properties. The sample is studied by high-resolution transmission electron microscopy (HRTEM), electron energy-loss spectroscopy (EELS), nuclear magnetic resonance (NMR), UV-visible and IR spectroscopy, electrochemistry and electrogenerated chemiluminescence (ECL). The results showed that the nanoparticles are constituted by a graphitic core surrounded by an amorphous layer, which seems to be significant in the determination of the optical and electronic properties observed in the system under study.

RESUMEN

A new dye, SSD1, featuring two donor/acceptor chromophores aligned in a spiro configuration with two anchoring groups separated at a distance of 10.05 A (closely matching the distance between the adsorption sites of the anatase TiO(2) surface) undergoes efficient dye adherence on TiO(2) films. A dye-sensitized solar cell incorporating SSD1 exhibited a short-circuit current of 8.9 mA cm(-2), an open-circuit voltage of 0.63 V, a fill factor of 0.67, and a power conversion efficiency of 3.75%.

RESUMEN

Spectroscopic and photodynamic properties of polymeric films bearing porphyrin units have been studied in both solution containing photooxidizable substrates and in vitro on Escherichia coli and Candida albicans microorganisms. The films were formed by electrochemical polymerization of 5,10,15,20-tetra(4-N,N-diphenylaminophenyl)porphyrin (H2P-film) and its complex with Pd(II) (PdP-film) on optically transparent indium tin oxide (ITO) electrodes. Absorption spectroscopic studies show the characteristic Soret and Q bands of the porphyrin in the visible region and a band at approximately 350 nm corresponding to the tetraphenylbenzidine units. Upon excitation, the H2P-film exhibits two bands of fluorescence emission from porphyrin, while it is not detected using PdP-film. The singlet molecular oxygen, O2(1Deltag), productions of these surfaces were evaluated using 9,10-dimethylanthracene in N,N-dimethylformamide. Also, the photodynamic activity was compared in solutions of L-tryptophan. Under these conditions, oxidation of these substrates takes place indicating an efficient photodynamic action of both polymeric films. In vitro investigations show that these films produce photosensitized inactivation of microbial cells in aqueous suspensions. These films exhibit a photosensitizing activity causing a approximately 3 log decrease of E. coil and approximately 2.5 log of C. albicans cellular survival after 30 min of irradiation with visible light. The photodynamic effect of the surfaces was also tested by growth delay experiments. The results indicate that porphyrins immobilized on electropolymeric films are interesting and versatile photodynamic surfaces to inactivate microorganisms in liquid suspensions.

Asunto(s)

Antiinfecciosos/farmacología , Polímeros/química , Porfirinas/química , Candida albicans/efectos de los fármacos , Candida albicans/crecimiento & desarrollo , Electroquímica , Escherichia coli/efectos de los fármacos , Escherichia coli/crecimiento & desarrollo , Fotoquímica , Polímeros/farmacología , Porfirinas/farmacología

RESUMEN

We report the synthesis and structural characterization of two dumbbell-shaped dendrimers incorporating 9-phenylcarbazole units as dendrons, as well as their thermal, morphological, photophysical, and electrochemical properties.

RESUMEN

Free-base (P), Zn(II) (P(Zn)), Cu(II) (P(Cu)), Pd(II) (P(Pd)), Ni(II) (P(Ni)), and Co(II) (P(Co)) 5-(4-carboxyphenyl)-10,15,20-tris(4-methylphenyl) porphyrins were designed and synthesized to be employed as spectral senzitizers in photoelectrochemical cells. The dyes were studied adsorbed on SnO(2) nanocrystalline semiconductor and also in Langmuir-Blodgett film ITO electrodes in order to disclose the effect of molecular packing on the studied properties. Electron injection yields were obtained by fluorescence quenching analysis comparing with the dyes adsorbed on a SiO(2) nanocrystalline insulator. Back electron-transfer kinetics were measured by using laser flash photolysis. The unmetallized and metallized molecules have different singlet state energies, fluorescence quantum yields, and redox properties. The quantum yields of sensitized photocurrent generation are shown to be highly dependent on the identity of the central metal. It is shown that P(Ni) and P(Co) do not present a photoelectric effect. The other porhyrins present reproducible photocurrent, P(Pd) being the one that gives the highest quantum yield even in closely packet ITO/LB films. Photocurrent quantum yields increase as the dye ground-state oxidation potential becomes more anodic, which is in agreement with the observation, obtained by laser flash photolysis, that back electron-transfer kinetics decrease with the increase in the driving force for the recombination process. This effect could be exploited as a design element in the development of new and better sensitizers for high-efficiency solar cells involving porphyrins and related dyes.