RESUMEN

The elucidation of the structure-property relationship is an important issue in the development of organic electronics. Combinatorial synthesis and the evaluation of systematically modified compounds is a powerful tool in the work of elucidating structure-property relationships. In this manuscript, D-π-A structure, 32 p-type organic semiconductors were rapidly synthesized via a one-pot, Suzuki-Miyaura coupling with subsequent Knoevenagel condensation. Evaluation of the solubility and photovoltaic properties of the prepared compounds revealed that the measured solubility was strongly correlated with the solubility parameter (SP), as reported by Fedors. In addition, the SPs were correlated with the Jsc of thin-film organic solar cells prepared using synthesized compounds. Among the evaluated photovoltaic properties of the solar cells, Jsc and Voc had strong correlations with the photoconversion efficiency (PCE).

Asunto(s)

RESUMEN

In this work, a simple and effective strategy to improve the photocatalytic dye degradation efficiency of the mesoporous-assembled TiO2 nanoparticle thin films by incorporating small contents of commercial P-25 TiO2 during the thin film preparation was developed. The mesoporous-assembled TiO2 nanoparticles were synthesized by a sol-gel method with the aid of a mesopore-directing surfactant, followed by homogeneously mixing with P-25 TiO2 prior to the thin film coating on glass substrate. The mesoporous-assembled TiO2 film with 5 wt.% P-25 TiO2 incorporation and calcined at 400°C provided an improved photocatalytic Acid Black (AB) dye degradation efficiency. The increase in number of coated layers to the optimum four layers of the aforementioned film was found to further improve the degradation efficiency. The recyclability test of this 5 wt.% P-25 TiO2-incorporated mesoporous-assembled TiO2 film with four coated layers revealed that it can be reused for multiple cycles without a requirement of post-treatment while the degradation efficiency was retained.

RESUMEN

This work focused on the improvement of the photocatalytic activity for Congo Red (CR) azo dye degradation of mesoporous-assembled 0.95 TiO2-0.05 In2O3 mixed oxide photocatalyst (with a TiO2-to-In2O3 molar ratio of 0.95:0.05) by loading with Ag nanoparticles. The mesoporous-assembled 0.95TiO2-0.05In2O3 mixed oxide photocatalyst was synthesized by a hydrolytic sol-gel method with the aid of a structure-directing surfactant, prior to loading with various Ag contents (0.5-2 wt.%) by a photochemical deposition method. The optimum Ag loading content was found to be 1.5 wt.%, exhibiting a great increase in photocatalytic CR dye degradation activity. The 1.5 wt.% Ag-loaded 0.95TiO2-0.05In2O3 mixed oxide photocatalyst was further applied for the CR dye degradation in the presence of water hardness. Different types (Ca2+ and Ca2+ -Mg2+ mixture) and concentrations (200 and 500 mg/l) of water hardness were investigated. The results showed that the water hardness reduced the photocatalytic CR dye degradation activity, particularly for the extremely hard water with 500 mg/l of Ca2+ -Mg2+ mixture. The adjustment of initial solution pH of the CR dye-containing hard water to an appropriate value was found to improve the photocatalytic CR dye degradation activity under the identical reaction conditions.

Asunto(s)

RESUMEN

We demonstrate that dimeric fullerene derivatives work as an excellent n-type material for polymer solar cells in combination with P3HT or PTB7, showing the best PCE of 3.3% or 6.1%, respectively. The device performance was influenced by the position of the two C60 moieties linked together.

RESUMEN

In an organic-based solar cell, the short exciton diffusion length of organic materials requires effective donor-acceptor heterojunction at the nanoscale. In this work, hybrid inorganic/polymer solar cells based on ZnO nanostructures and poly(3-hexylthiophene) (P3HT) are constructed to study the effects of ZnO morphologies and wettability of the surface on the P3HT infiltration ability and charge transport mechanisms. The P3HT infiltrates the ZnO nanorod (NR) more remarkably than ZnO nanoparticle (NP) substrates. Although surface modification with indoline D205 dye molecules improves the wettability (viz. enlarges the contact angle) of NP surface, the P3HT infiltration distance decreases in comparison with the pristine NP case. This leads to relatively low short-circuit current density (Jsc) of the NP devices in comparison with that of the NR devices, even though the surface area of NP layers is larger than that of NR ones. Moreover, surface modification with squaraine dye onto the NR surface shows more significant improvement in Jsc than the NP case. This is due to the well-aligned morphology of the NRs, which facilitates dye modification, P3HT infiltration, and charge transport processes. These indicate that the NRs are more qualified as electron accepting substrates and transport pathway in hybrid solar cells than NPs.

RESUMEN

SnS2 nanoparticles were synthesized through a simple wet chemical process at room temperature. The SnS2 nanoparticles were approximately spherical in shape and had diameter about 3-4 nm. SnS2-sensitized TiO2 electrodes were fabricated by the immersion of chemically modified TiO2 to well-dispersed SnS2 solution for 72 h (i.e., self-assembly method.) SnS2-sensitized TiO2 electrodes were applied in quantum dot-sensitized solar cells (QDSSCs). Under AM1.5 irradiation with 100 mW/cm2 light intensity (at 1 sun), the short-circuit current density (J(sc)), the open-circuit voltage (V(oc)), the fill factor (FF), and the energy conversion efficiency (eta) were 0.47 mA/cm2, 0.29 V, 0.58 and 0.081%, respectively.

Asunto(s)

RESUMEN

Modification of the σ-framework of [60]fullerene has been shown to be a new avenue toward n-type materials for bulk-heterojunction solar cells. This approach allowed distinct control of the LUMO level of the C(60)π-system and resulted in a clear improvement of an open-circuit voltage.

RESUMEN

SnS-sensitized TiO2 electrodes were applied in quantum dot-sensitized solar cells (QDSSCs) which are environmentally more favorable than conventional Cd or Pb-chalcogenide-sensitized electrodes. SnS nanoparticles were well-distributed over the surface of TiO2 nanoparticles by the successive ionic layer adsorption and reaction (SILAR) method. Deposited SnS nanoparticles had diameter about 3 nm. Under AM1.5 irradiation with 100 mW/cm2 light intensity (at 1 sun), the energy conversion efficiency of obtained cells reached a value of 0.21% (0.25 cm2) at SILAR coating cycles of 5. In addition, the photovoltaic performance was improved by additional ZnS coating on the surface of SnS-sensitized TiO2 electrodes.

Asunto(s)

RESUMEN

We propose new strategy to facilitate the fabrication of conjugated polymer fiber with higher oriented structures, which focused on electrospinning of a blend solution of regioregular poly(3-hexylthiophene) (rr-P3HT) and poly(vinyl pyrrolidone) (PVP). SEM observation revealed that the blend system forms homogeneous composite nanofibers. This system exhibits the specific feature of strong interchain contribution of P3HT from UV-vis absorption, fluorescence spectroscopic, XRD, and photoelectron spectrometric (for HOMO levels) investigations. We also demonstrate the removal of the PVP component from the P3HT/PVP composite fibers through the selective extraction and such strong interchain stacking of pristine P3HT fiber mat can be remarkably maintained.

RESUMEN

Vertically aligned single-crystalline TiO2 rutile nanorod arrays were synthesized on FTO transparent conductive substrates, via the hydrolysis of TiCl4 under the co-existence of amino acid catalysts. Using TiO2 seed nanocrystals (prepared from Ti(IV) ethoxide, calcined at 450 degrees C for 1 h), TiO, rutile nanorod arrays grew at a relatively mild temperature of 95 degrees C for 2 days. The growth speed and morphology of nanorod array were controllable by changing the type and concentration of amino acid. XRD analysis revealed that the TiO2 nanorod arrays were composed of highly crystalline rutile phase even without calcination. Preliminary dye-sensitized solar cell performance was also reported.

Asunto(s)

RESUMEN

The rational design of peptide and protein helices is not only of practical importance for protein engineering but also is a useful approach in attempts to improve our understanding of protein folding. Recent modifications of theoretical models of helix-coil transitions allow accurate predictions of the helix stability of monomeric peptides in water and provide new possibilities for protein design. We report here a new method for the design of alpha-helices in peptides and proteins using AGADIR, the statistical mechanical theory for helix-coil transitions in monomeric peptides and the tunneling algorithm of global optimization of multidimensional functions for optimization of amino acid sequences. CD measurements of helical content of peptides with optimized sequences indicate that the helical potential of protein amino acids is high enough to allow formation of stable alpha-helices in peptides as short as of 10 residues in length. The results show the maximum achievable helix content (HC) of short peptides with fully optimized sequences at 5 degrees C is expected to be approximately 70-75%. Under certain conditions the method can be a powerful practical tool for protein engineering. Unlike traditional approaches that are often used to increase protein stability by adding a few favorable interactions to the protein structure, this method deals with all possible sequences of protein helices and selects the best one from them.

Asunto(s)

RESUMEN

We report herein a simple procedure for the fabrication of TiO2 nanofibers by the combination of electrospinning and sol-gel techniques by using poly(vinylpyrrolidone) (PVP), titanium(IV) butoxide, and acetylacetone in methanol as a spinning solution. TiO2 nanofibers (260-355 nm in diameter), with a bundle of nanofibrils (20-25 nm in diameters) aligned in the fiber direction, or particle-linked structures were obtained from the calcination of as-spun TiO2/PVP composite fibers at temperatures ranging from 300 to 700 degrees C. These nanofibers were utilized as photocatalysts for hydrogen evolution. The nanofiber photocatalyst calcined at 450 degrees C showed the highest activity among the TiO2 nanofibers tested such as ones prepared by the hydrothermal method and anatase nanoparticles (Ishihara ST-01). These results indicate that one-dimensional electrospun nanofibers with highly aligned bundled nanofibrils are beneficial for enhancement of the crystallinity, large surface area, and higher photocatalytic activity.

Asunto(s)

RESUMEN

Electrode structures and photovoltaic properties of porphyrin-sensitized solar cells with TiO2 and Nb-, Ge-, and Zr-added TiO2 composite electrodes were examined to disclose the effects of partial substitution of Ti atom by the other metals in the composite electrodes. The TiO2 and Nb-, Ge-, and Zr-added TiO2 composite electrodes were prepared by sol-gel process using laurylamine hydrochloride as a template for the formation of micellar precursors yielding well-defined mesoporous nanocrystalline structures, as in the cases of the formation of silica and titania tubules and nanoparticles by the templating mechanism. The TiO2 and Nb-, Ge-, and Zr-added TiO2 composite electrodes were characterized by transmission electron microscopy, BET surface area analysis, X-ray diffraction analysis, Raman spectroscopy, and impedance measurements. The TiO2 anatase nanocrystalline structure is retained after doping a small amount (5 mol %) of Nb, Ge, or Zr into the TiO2 structure, suggesting the homogeneous distribution of the doped metals with replacing Ti atom by the doped metal. The power conversion efficiency of the porphyrin-sensitized solar cells increases in the order Zr-added TiO2 (0.8%) < Nb-added TiO2 (1.2%) < TiO2 (2.0%) < Ge-added TiO2 cells (2.4%) under the same conditions. The improvement of cell performance of the Ge-added TiO2 cell results from the negative shift of the conduction band of the Ge-added TiO2 electrode. The Ge-added TiO2 cell exhibited a maximum power conversion efficiency of 3.5% when the porphyrin was adsorbed onto the surface of the Ge-added TiO2 electrode with a thickness of 4 microm in MeOH for 1 h.

RESUMEN

A simple route of combined sol-gel process with surfactant-assisted templating technique was successfully employed for the first time to synthesize nanocrystalline mesoporous Dy(2)O(3) with narrow monomodal pore size distribution under mild conditions. The nanocrystalline Dy(2)O(3) with monomodal mesoporous characteristic was ultimately achieved by controlling the hydrolysis and condensation steps of dysprosium n-butoxide modified with acetylacetone in the presence of laurylamine hydrochloride surfactant aqueous solution. The synthesized material was methodically characterized by thermogravimetry and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), N(2) adsorption-desorption, Brunauer-Emmett-Teller (BET) surface area analysis, and Barrett-Joyner-Halenda (BJH) pore size distribution analysis. The particle size of the synthesized Dy(2)O(3) in nanosized range obtained from the SEM and HRTEM micrographs was in good accordance with the crystallite size estimated from the XRD result. The N(2) adsorption-desorption result exhibited hysteresis pattern with single loop, indicating the existence of monomodal mesopore. The extremely narrow pore size distribution with mean pore diameter in the mesopore region of the synthesized Dy(2)O(3) was also confirmed by the BJH result.

RESUMEN

High surface area nanosheet TiO2 with mesoporous structure were synthesized by hydrothermal method at 130 degrees C for 12 h. The samples characterized by XRD, SEM, TEM, SAED, and BET surface area. The nanosheet structure was slightly curved and approximately 50-100 nm in width and several nanometers in thickness. The as-synthesized nanosheet TiO2 had average pore diameter about 3-4 nm. The BET surface area and pore volume of the sample were about 642 m(2)/g and 0.774 cm(3)/g, respectively. The nanosheet structure after calcinations were changed into nanorods/nanoparticles composite with anatase TiO2 structure at 300-500 degrees C (10-15 nm in rods diameter and about 5-10 nm in particles diameter). The solar energy conversion efficiency (eta) of the cell using nanorods/nanoparticles TiO2 (from the nanosheet calcined at 450 degrees C for 2 h) with mesoporous structure was about 7.08% with Jsc of 16.35 mA/cm(2), Voc of 0.703 V and ff of 0.627; while eta of the cell using P-25 reached 5.82% with Jsc of 12.74 mA/cm(2), Voc of 0.704 V, and ff of 0.649.

Asunto(s)

RESUMEN

Sequence-specific DNA binding of short peptide dimers derived from a plant basic leucine zipper protein EmBP1 was studied. A homodimer of the EmBP1 basic region peptide recognized a palindromic DNA sequence, and a heterodimer of EmBP1 and GCN4 basic region peptides targets a non-palindromic DNA sequence when a beta-cyclodextrin/adamantane complex is utilized as a dimerization domain. A homodimer of the EmBP1 basic region peptide binds the native EmBP1 binding 5'-GCCACGTGGC-3' and the native GCN4 binding 5'-ATGACGTCAT-3' sequences with almost equal affinity in the alpha-helical conformation, indicating that the basic region of EmBP1 by itself has a dual recognition codes for the DNA sequences. The GCN4 basic region peptide binds 5'-ATGAC-3' in the alpha-helical conformation, but it neither shows affinity nor helix formation with 5'-GCCAC-3'. Because native EmBP1 forms 100 times more stable complex with 5'-GCCACGTGGC-3' over 5'-ATGACGTCAT-3', our results suggest that the sequence-selectivity of native EmBP1 is dictated by the structure of leucine zipper dimerization domain including the hinge region spanning between the basic region and the leucine zipper.

Asunto(s)

RESUMEN

Tools for selective recognition and sensing of kinase-catalyzed phosphorylation of Tyr or Ser/Thr residues located on a protein surface are essential for understanding signal transduction cascades of living cell. A stable complex of RNA and peptide (ribonucleopeptide) provides a new approach to tailor a receptor for small molecules. In vitro selection of an RNA-derived pool of ribonucleopeptide afforded a ribonucleopeptide receptor specific for phosphotyrosine (pTyr). Moreover, the ribonucleopeptide receptors are conveniently converted to fluorescent sensors for pTyr.

Asunto(s)

RESUMEN

The introduction of a flavin chromophore on the myoglobin (Mb) surface and an effective electron-transfer (ET) reaction through the flavin were successfully achieved by utilizing the self-assembly of heterostranded coiled-coil peptides. We have prepared a semiartificial Mb, named Mb-1alphaK, in which an amphiphilic and cationic alpha-helix peptide is conjugated at the heme propionate (Heme-1alphaK). Heme-1alphaK has a covalently bound iron-protoporphyrin IX (heme) at the N terminus of a 1alphaK peptide sequence. This sequence was designed to form a heterostranded coiled-coil in the presence of a counterpart amphiphilic and anionic 1alphaE peptide sequence in a parallel orientation. Two peptides, Fla(1)-1alphaE and Fla(31)-1alphaE, both incorporating a 10-methylisoalloxazine moiety as an artificial flavin molecule, were also prepared (Fla=2-[7-(10-methyl)isoalloxazinyl]-2-oxoethyl). Heme-1alphaK was successfully inserted into apomyoglobin to give Mb-1alphaK. Mb-1alphaK recognized the flavin-modified peptides and a two-alpha-helix structure was formed. In addition, an efficient ET from reduced nicotinamide adenine dinucleotide to the heme center through the flavin unit was observed. The ET rate was faster in the presence of Fla(1)-1alphaE than in the presence of Fla(31)-1alphaE or the equivalent molecule that has no peptide chain. These results demonstrate that the introduction of a functional chromophore on the Mb surface can be achieved by using specific peptide-peptide interactions. Moreover, the dependence of the ET rate on the position of the flavin indicated that the distance between the heme active site and the flavin chromophore was regulated by the three-dimensional structure of the designed polypeptide.

Asunto(s)

RESUMEN

Selection of functional RNAs from randomized pool of RNA molecules successfully affords RNA aptamers that specifically bind to small molecules, and that have catalytic activities. Recent structural analyses of the ribosomal RNA complex suggest that the RNA-protein complex would be a new structural candidate for the design of tailor-made receptors and enzymes. We have designed an ATP binding domain that consists of an RNA subunit and a peptide subunit by means of structure-based design approach and successive in vitro selection method. The RNA subunit is designed to consist of two functional domains; an ATP binding domain with 20 randomized nucleotides and an adjacent stem region that serves as a binding site for the RNA-binding peptide. The randomized nucleotide region was placed next to the HIV-1 Rev response element to enable the formation of "ribonucleopeptide" pools in the presence of the Rev peptide. In vitro selection of RNA oligonucleotides from the randomized pool afforded a ribonucleopeptide receptor specific for ATP. The ATP-binding ribonucleopeptide did not share the known consensus nucleotide sequence for ATP aptamers, and completely lost its ATP-binding ability in the absence of the Rev peptide. The ATP-binding activity of the ribonucleopeptide was increased by a substitution of the N-terminal amino acid of the Rev peptide. These results demonstrate that the peptide stabilizes the functional structure of RNA and suggest that amino acids outside the RNA binding region of the peptide participate in the ATP binding. Our approach would provide a new strategy for the design of tailor-made ribonucleopeptide receptors.

Asunto(s)

RESUMEN

Here we report a simple method to convert synthetic receptors to fluorescent sensors. An RNA-peptide complex (ribonucleopeptide) with a known three-dimensional structure is used as a framework of the receptor. Artificial ribonucleopeptide sensors were created with a combination of in vitro selection method and successive modification of the peptide with a fluorophore. A ribonucleopeptide complex of the fluorophore labeled peptide showed a remarkable fluorescence emission change upon binding cognate ligands.

Asunto(s)