High-performance, room-temperature (RT), solid-state dye-sensitized solar cells (DSSCs) were fabricated using hierarchically structured TiO₂ nanofiber (HS-NF) electrodes and plastic crystal (PC)-based solid-state electrolytes. The electrospun HS-NF photoelectrodes possessed a unique morphology in which submicrometer-scale core fibers are interconnected and the nanorods are dendrited onto the fibers. This nanorod-in-nanofiber morphology yielded porosity at both the mesopore and macropore level. The macropores, steming from the interfiber space, afforded high pore volumes to facilitate the infiltration of the PC electrolytes, whereas the mesoporous nanorod dendrites offered high surface area for enhanced dye loading. The solid-state DSSCs using HS-NFs (DSSC-NF) demonstrated improved power conversion efficiency (PCE) compared to conventional TiO₂ nanoparticle (NP) based DSSCs (DSSC-NP). The improved performance (>2-fold) of the DSSC-NFs was due to the reduced internal series resistance (R(s)) and the enhanced charge recombination lifetime (τ(r)) determined by electrochemical impedance spectroscopy and intensity modulated photocurrent/photovoltage spectroscopy. The easy penetration of the PC electrolytes into HS-NF layers via the macropores reduces R(s) significantly, improving the fill factor (FF) of the resulting DSSC-NFs. The τ(r) difference between the DSSC-NF and DSSC-NP in the PC electrolytes was extraordinary (~14 times) compared to reported results in conventional organic liquid electrolytes. The optimized PCE of DSSC-NF using the PC electrolytes was 6.54, 7.69, and 7.93% at the light intensity of 100, 50, and 30 mW cm⁻², respectively, with increased charge collection efficiency (>40%). This is the best performing RT solid-state DSSC using a PC electrolyte. Considering the fact that most reported quasi-solid state or nonvolatile electrolytes require higher iodine contents for efficient ion transport, our HS-NFs are a promising morphology for such electrolytes that have limited ion mass transport.

Water-soluble, polyelectrolyte-grafted multiwalled carbon nanotubes (MWCNTs), MWCNT-g-PSSNa, were synthesized using a "grafting to" route. MWCNT-g-PSSNa thin films fabricated by an electrostatic spray (e-spray) technique were used as the counter electrode (CE) for dye-sensitized solar cells (DSSCs). The e-sprayed MWCNT-g-PSSNa thin-film-based CEs (MWCNT-CE) were uniform over a large area, and the well-exfoliated MWCNTs formed highly interconnected network structures. The electrochemical catalytic activity of the MWCNT-CE at different thicknesses was investigated. The MWCNT-g-PSSNa thin film showed high efficiency as a CE in DSSCs. The power conversion efficiency (PCE) of the DSSCs using the MWCNT-g-PSSNa thin-film-based CE (DSSC-MWCNT) was >6% at a CE film thickness of approximately 0.3 microm. The optimum PCE was >7% at a film thickness of approximately 1 microm, which is 20-50 times thinner than conventional carbon-based CE. The charge transfer resistance at the MWCNT-CE/electrolyte interface was 1.52 Omega cm(2) at a MWCNT-CE thickness of 0.31 microm, which is lower than that of a Pt-CE/electrolyte interface, 1.78 Omega cm(2). This highlights the potential for the low-cost CE fabrication of DSSCs using a facile deposition technique from an environmentally "friendly" solution at low temperatures.

Hexakis(pentafluorophenyl)-substituted meso-meso-linked Zn(II)-diporphyrin (9), which was prepared by the acid-catalyzed cross-condensation of 1,1,2,2-tetrapyrroethane (5) with dipyrromethane dicarbinol (6), was converted into meso-meso,β-β,β-β triply linked Zn(II)-diporphyrin 3 by oxidation with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) and Sc(OTf)(3). Beside the red-shifted absorption spectrum and split first oxidation potential that are common to the triply-linked Zn(II)-diporphyrins, diporphyrin 3 exhibited considerably improved chemical stability owing to a lowered HOMO and good solubility in common organic solvents. The two-photon absorption (TPA) cross-section and S(1)-state lifetime of compound 3 were 1700 GM and 3.3 ps, respectively.

Optimal responses during imatinib therapy are commonly defined following the European LeukemiaNet (ELN) recommendations. Achievements of these optimal responses have not, however, been comprehensively tested as response-related prognostic factors using single center data sets. We evaluated the parameters using long-term (median 63 months) outcomes from 363 chronic phase chronic myeloid leukemia patients treated with imatinib as frontline therapy at our center. Intention-to-treat analysis showed comparable rates of complete cytogenetic response (86 %), major molecular response (MMR, 54 %), and complete molecular response (MR(4.5), 8 %). Estimated overall survival, progression-free survival, and event-free survival at 7 years were 94, 88 and 84 %, respectively. Achievement of recommended optimal response at 6 months (major cytogenetic response) and 12 months (complete cytogenetic response) yielded significantly better overall, progression-free, and event-free survival. However, achievement of recommended optimal response at 18 months (MMR) provided marginal benefit only in event-free survival. Most ELN criteria were predictive of long-term outcomes, with the exception of the clinical significance of achieving MMR at 18 months. Treatment adherence in the early treatment period was one of the important independent predictors of favorable long-term outcome. Durable cytogenetic and molecular responses were maintained in a majority of patients treated with optimal dose intensity.

A new type of porphyrin ligand bearing four triazole groups at the ortho-positions of phenyl rings in tetraphenylporphyrin was synthesized for the formation of monoporphyrinate lanthanide complexes without ancillary ligands.

In Salmonella enterica serovar Typhimurium, many of the genes required for intestinal penetration and invasion of host cells are encoded within the Salmonella pathogenicity island 1 (SPI1). The expression of invF, which is a positive transcriptional activator of SPI1, is controlled by HilA-dependent (invF-1) and HilC/D-dependent (invF-2) promoters. Transcriptional analysis of invF revealed that the invF-2 promoter (P(invF-2)) was not activated when cells were grown in standing culture conditions (which are known to induce SPI1) and that hilD mutation decreased the expression of P(invF-2) only in shaking culture conditions. In the absence of invF-1 promoter (P(invF-1)), P(invF-2) promoted InvF production and sipC expression (which is regulated by InvF) in shaking culture conditions. An analysis of the transcription patterns of plasmids harboring the lacZY reporter gene under various P(invF-2) derivatives with truncations or mutations revealed that the downstream region of the P(invF-2) transcription start site (i.e., +148 to +363) plays a role in repressing P(invF-2) in standing culture and in HilD-dependent activation of P(invF-2) in shaking culture conditions. The expression of invH overlaps with P(invF-2), but they are transcribed in opposite directions. However, invH expression did not influence P(invF-2) activity. This suggests that independent regulation of the two invF promoters allows Salmonella to respond quickly to environmental changes.

We have investigated the single-molecule fluorescence dynamics of a butadiyne-linked porphyrin dimer (Z2B) depending on the density of the poly(methyl methacrylate)(PMMA) matrix (5, 10, 25, and 50 mg ml(-1)). By recording single-molecule fluorescence intensity trajectories and fluorescence lifetimes, we observed more frequent one-step photobleaching behavior, less frequent on-off behavior, and narrower fluorescence lifetime distributions in lower densities of PMMA polymer. In contrast, more enhanced photostability was observed in higher densities of PMMA polymer. These results are explained by a difference in the molecular surroundings depending on the change in PMMA polymer density, suggesting that the individual photophysical properties of Z2B are strongly associated with their conformations and molecular surroundings in the solid state. Our studies will provide further information on the structure/surroundings relationship of single molecules in the solid state.

A new member of the cyclo[n]pyrrole class of expanded porphyrins could be prepared from the corresponding thiophene-containing terpyrrole precursor through use of a mild electrochemical oxidative procedure. The isolated macrocycle, featuring nine heterocyclic subunits directly connected through their α,α'-positions, is the largest cyclo[n]pyrrole derivative reported to date.

It has been demonstrated that the direction and magnitude of transition dipole moments, and hence rates in the excitation energy hopping in the self-assembled porphyrin boxes can be tuned by insertion of ethynyl groups as well as the dielectric constant of solvent.

A two-electron oxidation of the Cu(II)(9) and Zn(II)(12) complexes of tetraphenyltetrabenzoporphyrin (TPTBP) results in the formation of stable antiaromatic [(TPTBP)Cu(II)(H(2)O)](2+)⋅2 [SbF(6)](-)(10) and [(TPTBP)Zn(II)(H(2)O)(2)](2+)⋅2 [SbF(6)](-)(13) with 16π electrons on the inner ligand perimeter. X-ray structures of the parent TPTBP complexes, the dications, and singly oxidized species [(TPTBP)Cu(II)](⋅+)[SbF(6)](-)(11) reveal that the use of TPTBP rather than a porphyrin ligand reduces the degree of nonplanarity in the 16π-electron species relative to the parent 18π complex. Significant high-field shifts of the (1)H NMR signals of the outer ring protons and large positive values in calculations of nucleus-independent chemical shifts on the central cavity of the porphyrin ring provide unambiguous evidence for the antiaromatic character of the 16π Zn(II) species. A combination of magnetic circular dichroism spectroscopic studies and TD-DFT calculations on both the Zn(II) and Cu(II) species demonstrates that the main electronic bands of the dicationic species can be readily assigned by using Michl's 4N perimeter model. Femtosecond transient absorption studies clearly demonstrated that the number of π electrons on the inner ligand perimeter and the configuration of the central metal ion play a critical role in the excited-state relaxation dynamics. Redox potentials for conversion between the 16π, 17π, and 18π systems were measured by cyclic voltammetry in dichloromethane and benzonitrile, and UV/Vis spectra of each oxidation/reduction product were monitored by thin-layer spectroelectrochemistry.

The light harvesting efficiency of dye-sensitized solar cells was enhanced by using a scattering layer. Such as sphere type TiO2, inverse photonic crystal TiO2, hollow spherical TiO2. Among these materials, the TiO2 with inverse photonic crystal (IPC) structure, synthesized by self-assembly using spherical templates, has attracted much attention due to their photonic crystal characteristics and light scattering effects. However, when applied in the DSSCs, the surface area of IPC is very low that caused insufficient adsorption amount of dye molecules. In the present work, a scattering layer with mesoporous inverse photonic crystal (MIPC) TiO2 film was fabricated by the sol-gel reactions with surfactant-assisted sol-gel method using poly(methyl methacrylate) as the template and titanium (IV) isopropoxide as the TiO2 precursor. After removing the PMMA and surfactant, a highly ordered macroporous structure with mesopores were successfully obtained. The surface area and total pore volume of the MIPC were 82 m2/g and 0.31 cm3/g, respectively, which is much larger than those of the IPC. The DSSCs with the scattering layer of MIPC film exhibited 18 and 10% higher photo-conversion efficiency than those of cells only with a nano-crystalline TiO2 film and with scattering layer of IPC film. From UV-visible spectra of dye solutions, the MIPC film showed a higher amount of absorbed dye molecules than those of the reference and IPC films. Accordingly, an increase in the photo-current density through abundant adsorption of the dye, coupled with inherent light scattering ability can improve overall photo-conversion efficiency.

We report the preparation of highly interconnected ordered mesoporous carbon-carbon nanotube nanocomposites which show Pt-like dye-sensitized solar cell (DSSC) efficiency and remarkable long-term durability as DSSC counter electrodes.

TiO2 films were prepared on glass substrates using the sol-gel process for a dye-sensitized solar cell application. The TiO2 sol was prepared using hydrolysis/polycondensation. Titanium (IV) Tetra Isopropoxide (TTIP) was used as precursor and Nitric acid (HNO3) was used as a catalyst for the peptization. The crystal structure and morphology of the prepared materials were characterized by XRD, and an SEM. The observations confirmed the nanocrystalline nature of the TiO2. The reaction parameters, such as the catalyst concentrations, the calcination time, and the calcination temperature were varied during the synthesis in order to achieve nanosize TiO2 particles. The prepared TiO2 particles were coated onto FTO glass using a screen printing technique. The prepared TiO2 films were characterized by UV-vis. The TiO2 particles calcinated at low temperatures showed an anatase phase they grew into a rutile phase when the calcination temperature increased. The size and structure of the TiO2 particles were adjusted to specific surface areas. It was found that the conversion efficiency of the DSSC was highly affected by the properties of the TiO2 particles.

ABSTRACT: Cu2ZnSnSe4 (CZTSe) nanoparticles with diameters of 200-300 nm were synthesized by one-step solvothermal method without surfactants or templates. The structure, composition and morphology of CZTSe nanoparticles were characterized by XRD, XPS, Raman spectrum, EDS, FESEM and TEM. The results indicated that the nanoparticles were single phase and nearly stoichiometric composition. CZTSe nanoparticles drop-casted onto FTO substrate were used as counter electrode (CE) in dye-sensitized solar cells (DSSCs) for the first time, which exhibited Pt-like electrocatalytic activity for the reduction of I3- to I- in DSSCs. The J-V results demonstrated that the thickness of the film affected the photocurrent density and fill factor remarkably, which was resulted from the difference of electrocatalytic sites and resistance with different thickness films. And a best efficiency of 3.85 % was obtained by adjusting the film thickness. The work presents a new approach for developing low-cost, facile fabrication CZTSe nanoparticles, and demonstrates CZTSe can be explored as a low-cost alternative for expensive and scare Pt in DSSCs.

A type of highly efficient completely flexible fiber-shaped solar cell based on TiO(2) nanotube array is successfully prepared. Under air mass 1.5G (100 mW cm(-2)) illumination conditions, the photoelectric conversion efficiency of the solar cell approaches 7%, the highest among all fiber-shaped cells based on TiO(2) nanotube arrays and the first completely flexible fiber-shaped DSSC. The fiber-shaped solar cell demonstrates good flexibility, which makes it suitable for modularization using weaving technologies.

Three novel 2,6-modified Bodipy sensitizers were synthesized and evaluated for their use in dye-sensitized solar cells (DSSCs). Among them, dye B3, which carries a n-pentyl group at position 8, exhibits the best solar energy conversion efficiency (1.83 %). The results of this study provide a new strategy for the design of Bodipy derivatives as sensitizers for DSSCs.

Zn(2)SnO(4) nanoparticles (NPs) with a narrow size distribution were synthesized by a simple hydrothermal route by controlling the crystallization process. The average size of NPs was 8 nm, and this was attributed to the formation of a hydroxy carbonate compound as an intermediate phase, which was demonstrated by the structural and elemental analyses. The fine size and visible-transparency of the synthesized NPs enabled the fabrication of transparent films for efficient photoelectrochemical devices. In particular, we demonstrated dye-sensitized solar cells (DSSCs) employing these transparent Zn(2)SnO(4) photoelectrodes with a high energy conversion efficiency of 4.7%, which is mainly due to an improvement of light harvesting property.

In this study, nanocrystalline Nb2O5 thin film has been prepared via sol-gel process using niobium ethoxide as a precursor. Sol-gel films using various ratios of H2O/Nb have been prepared on fluorinated tin oxide (FTO) glass substrate, and used as electron-blocking layer of dye-sensitized solar cell (DSSC). The Nb2O5 film as deposited was amorphous, but became crystalline with hexagonal phase after heat treatment at 600 degrees C. With higher H2O/Nb molar ratio, denser and more uniform Nb2O5 film surface was obtained. DSSCs with the structure of FTO/Nb2O5/TiO2/Dye/EL/Pt/FTO have been prepared, and their solar-cell performance was evaluated. By introduction of Nb2O5 sol-gel film between FTO and TiO2 layer in DSSCs, energy conversion efficiency could be improved.

A new I(-)/(SeCN)(2) redox mediator has favorable properties for dye-sensitized solar cells (DSCs) such as less visible light absorption, higher ionic conductivity, and downward shift of redox potential than I(-)/I(3)(-). It was then applied for DSCs towards increasing energy conversion efficiency, giving a new potential for improving performance.

A novel heterostructural TiO(2) nanocomposite, which consists of single-crystalline rutile TiO(2) nanorod decorated Degussa P25 nanoparticles, has been fabricated through a facile acidic hydrothermal method and successfully applied as the photoanodes for efficient dye-sensitized solar cells. The morphology, crystal structure, specific surface area and pore size distribution of the obtained nanocomposite were systematically investigated by X-ray diffraction (XRD), field-emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM), selected-area electron diffraction patterns (SAED) and nitrogen adsorption-desorption measurements. Under standard illumination conditions (AM 1.5, 100 mW cm(-2)), devices with these hybrid anodes exhibited considerably enhanced photocurrent density and overall conversion efficiency in comparison with that of the commercial Degussa P25 electrodes, which can be partially attributed to the light scattering effect in the long-wavelength region as evidenced from the incident photon-to-current conversion efficiency (IPCE) response and the diffuse reflectance spectroscopy. More importantly, devices employing these hybrid anodes have demonstrated extended electron lifetimes and larger electron diffusion coefficient as validated by the intensity-modulated photocurrent/photovoltage spectroscopy measurements, which can be mainly ascribed to the fast electron transport and collection superiority of the single-crystalline nanorods.