Improving Microstructured TiO2 Photoanodes for Dye Sensitized Solar Cells by Simple Surface Treatment

TiCl₄ surface treatment studies of porous electrode structure of TiO₂ aggregates synthesized using an acidic precursor and CTAB as a templating agent are carried out in order to understand and improve upon recombination kinetics in the photonanode film matrix, together with enhancing the intrinsic light scattering. The key beneficial features of the photoanode included high surface roughness, necessary for superior dye adsorption, nanocrystallite aggregates leading to diffuse light scattering within the film matrix, and a hierarchical macro‐ and mesopore structure allowing good access of electrolyte to the dye, thereby assisting in dye regeneration (enhanced charge transfer). Pre‐treatment of the TiO₂ electrodes reduced recombination at the fluorine‐doped tin oxide (FTO)/electrolyte interface. The post‐treatment study showed enhanced surface roughness through the deposition of a thin overlayer of amorphous TiO₂ on the film structure. This led to a notable improvement in both dye adsorption and inherent light scattering effects by the TiO₂ aggregates, resulting in enhanced energy harvesting. The thin TiO₂ overlayer also acted as a barrier in a core‐shell configuration within the porous TiO₂ matrix, and thereby reduced recombination. This allowed the hierarchical macro‐ and mesoporosity of the film matrix to be utilized more effectively for enhanced charge transfer during dye regeneration. Post‐treatment of the aggregated TiO₂ matrix resulted in a 36% enhancement in power conversion efficiency from 4.41% of untreated cells to 6.01%.     

Dye-sensitized photocurrents and adsorption properties of merocyanine dye at atomically flat rutile (1 1 0) and (1 0 0) TiO2 surfaces

The crystal-face dependence of the dye-sensitized photocurrents and the adsorption properties of benzothiazole merocyanine (Mc[18,1]) dye molecules were investigated, using atomically flat (1 0 0) and (1 1 0) TiO₂ single crystal surfaces. From the estimation of the amount of the transferred charge from the TiO₂ surface to CO groups of dye molecules based on NEXAFS data, it was revealed that the interaction of the adsorbed molecules and the (1 1 0) surface was much stronger than that for the (1 0 0) surface. On the other hand, the absorbed photon to current conversion efficiency (APCE) value was almost the same for both surfaces. We suggested a possible explanation as follows: the energy difference between the LUMO of Mc[18,1] and the conduction band of TiO₂ was large enough to give a nearly 100% quantum efficiency of electron transfer from photoexcited dye to TiO₂, which made the difference in the interaction between dye molecules and TiO₂ not apparent. The incident photon to current conversion efficiency (IPCE) for the (1 0 0) surface was much larger than that for the (1 1 0) surface, which was explained by the fact that the amount of the adsorbed dye molecules on the (1 0 0) surface was larger than on the (1 1 0) surface, probably due to the larger surface density of five-coordinated Ti sites in the former surface.     

Modified nano-TiO2 coupled with fluorescence spectroscopy for the separation/analysis of l-tryptophan

A novel adsorbent of carboxymethyl-β-cyclodextrin modified nanometer TiO₂ (CM-β-CD/TiO₂) was prepared and used as a solid-phase extraction (SPE) material coupled to fluorescence spectroscopy determination of l-tryptophan (l-Trp) in biological samples. The experimental conditions for modified nanometer TiO₂ separation/preconcentration of l-Trp were optimized. The adsorption capacity of CM-β-CD/TiO₂ for l-Trp was 75.2 μg/g. The linear range, detection limit (DL), and the relative standard deviation (RSD) were 0.10-1.20 μg/mL, 18.8 ng/mL, and 0.67% (n = 3, 1.0 μg/mL), respectively, with a preconcentration factor of 10. The developed method was applied to determination of l-Trp in real samples and the recoveries were found to be in the range of 99.2-100.3%. For validation, a comparison material of NIC-140686 sample was analyzed and the determined value was in good agreement with the certified value.     

Efficient sensitization of nanocrystalline TiO2 films with high molar extinction coefficient ruthenium complex

A novel heteroleptic polypyridine ruthenium complex, cis-Ru(L1)(L2)(NCS)₂, L1 = 4,4′-dicarboxylic acid-2,2′-bipyridine (dcbpy), L2 = 4,4′-bis[p-diethylamino]-α-styryl]-2,2′-bipyridine, was synthesized. The dye displays extremely high molar extinction coefficient, which is comparable with organic dye. Preliminary test shows the dye-sensitized TiO₂ solar cell gives high conversion efficiency up to 8.65% under 1 Sun, while 8.35% is given for N3 based DSCs under the same condition. The dye will be further employed in solid state DSCs with hole transport material.     

Overcoming Charge Collection Limitation at Solid/Liquid Interface by a Controllable Crystal Deficient Overlayer

Bulk and surface charge recombination of photoelectrode are two key processes that significantly hinder solar‐to‐fuel conversion of photoelectrochemical cell (PEC). In this study, the function of a “crystal‐deficient” overlayer is unveiled, which outperforms a traditionally used amorphous or crystalline overlayer in PEC water splitting by exhibiting a high conductivity and large electron diffusion length to enable unlimited electron collection. The optimized ≈2.5 nm thickness of the “crystal‐deficient” shell results in a depletion layer with a width of 3 nm, which overcomes the flat band limitation of the photovoltage and increases the light absorptivity in the wavelength range from 300 to 420 nm. In addition, a 50‐fold increase in the conductivity yields a one‐order‐of‐magnitude increase in the diffusion length of an electron (L_n )(≈20 μm), allowing for unlimited electron collection in the 1.9 μm TiO₂ nanowire array with the “crystal‐deficient” shell. The controllable “crystal‐deficient” overlayer in rutile TiO₂ nanowires photoanode achieves a photocurrent density greater than 2.0 mA cm^?2 at 1.23 V versus reversible hydrogen electrode (RHE), a 1.18% applied bias photon‐to‐current efficiency at 0.49 V versus RHE, a faradaic efficiency greater than 93.5% at 0.6 V versus Pt under air mass 1.5G simulated solar light illumination (100 mW cm^?2).     

Efficient Nanostructured TiO2/SnS Heterojunction Solar Cells

Tin sulfide (SnS) is one of the most promising solar cell materials, as it is abundant, environment friendly, available at low cost, and offers long‐term stability. However, the highest efficiency of the SnS solar cell reported so far remains at 4.36% even using the expensive atomic layer deposition process. This study reports on the fabrication of SnS solar cells by a solution process that employs rapid thermal treatment for few seconds under Ar gas flow after spin‐coating a precursor solution of SnCl₂ and thiourea dissolved in dimethylformamide onto a nanostructured thin TiO₂ electrode. The best‐performing cell exhibits power conversion efficiency (PCE) of 3.8% under 1 sun radiation conditions (AM1.5G). Moreover, secondary treatment using SnCl₂ results in a significant improvement of 4.8% in PCE, which is one of the highest efficiencies among SnS‐based solar cells, especially with TiO₂ electrodes. The thin film properties of SnS after SnCl₂ secondary treatment are analyzed using grazing‐incidence wide‐angle X‐ray scattering, and high‐resolution transmittance electron microscopy.     

Nitrogen uptake responses of Gracilaria vermiculophylla (Ohmi) Papenfuss under combined and single addition of nitrate and ammonium

The ammonium (NH₄⁺) and nitrate (NO₃⁻) uptake responses of tetrasporophyte cultures from a Portuguese population of Gracilaria vermiculophylla were studied. Thalli were incubated at 5 nitrogen (N) levels, including single (50 μM of NH₄⁺ or NO₃⁻) and combined addition of each of the N sources. For the combined additions, the experimental conditions attempted to simulate 2 environments with high N availability (450 μM NO₃⁻ + 150 μM NH₄⁺; 250 μM NO₃⁻ + 50 μM NH₄⁺) and the mean N concentrations occurring at the estuarine environment of this population (30 μM NO₃⁻ + 5 μM NH₄⁺). The uptake kinetics of NH₄⁺ and NO₃⁻ were determined during a 4 h time-course experiment with N deprived algae. The experiment was continued up to 48 h, with media exchanges every 4 h. The uptake rates and efficiency of the two N sources were calculated for each time interval. For the first 4 h, G. vermiculophylla exhibited non-saturated uptake for both N sources even for the highest concentrations used. The uptake rates and efficiency calculated for that period (V_0-4 h), respectively, increased and decreased with increasing substrate concentration. NO₃⁻ uptake rates were superior, ranging from 1.06 ± 0.1 to 9.65 ± 1.2 μM g(dw)⁻¹ h⁻¹, with efficiencies of 19% to 53%. NH₄⁺ uptake rates were lower (0.32 ± 0.0 to 5.75 ± 0.08 μM g(dw)⁻¹ h⁻¹) but G. vermiculophylla removed 63% of the initial 150 μM and 100% at all other conditions. Uptake performance of both N sources decreased throughout the duration of the experiment and with N tissue accumulation. Both N sources were taken up during dark periods though with better results for NH₄⁺. Gracilaria vermiculophylla was unable to take up NO₃⁻ at the highest concentration but compensated with a constant 27% NH₄⁺ uptake through light and dark periods. N tissue accumulation was maximal at the highest N concentration (3.9 ± 0.25% dw) and superior under NH₄⁺ (3.57 ± 0.2% dw) vs NO3 (3.06 ± 0.1% dw) enrichment. The successful proliferation of G. vermiculophylla in estuarine environments and its potential utilization as the biofilter component of Integrated Multi-Trophic Aquaculture (IMTA) are discussed.     

The Electrostatic Interactions Between Nano-TiO<Subscript>2</Subscript> and Trypsin Inhibit the Enzyme Activity and Change the Secondary Structure of Trypsin

In this work, the interaction between nano-TiO₂ and trypsin was investigated, and the mechanisms of the interaction were explored by the methods of UV–vis detection, circular dichroism (CD), and fluorescence. The results clearly demonstrated that nano-TiO₂ had an inhibitory effect on the enzyme activity. The activity was decreased to 64% of the untreated trypsin in the presence of 300 μg/ml nano-TiO₂. UV spectrometry proved that nano-TiO₂ had a strong physical absorption effect on trypsin, and the CD spectra revealed that the secondary structure of trypsin was partly destroyed while bound together with nano-TiO₂. The ratio of α-helix increased from 7.9% to 12.8% in the presence of 100 μg/ml TiO₂ while the ratio of β-sheet decreased from 48.7% to 36.4%. Furthermore, the fluorescence spectrometry indicated that nano-TiO₂ could quench the intrinsic fluorescence of trypsin through static quenching. Meanwhile, the binding constant was calculated to be 1, and the process of binding of trypsin on nano-TiO₂ was a spontaneous molecular interaction procedure in which electrostatic interaction plays a major role. Our study was to provide a useful approach for evaluating the health risk of nanomaterials on level of proteins.     

Solution‐Processed TiO2 Nanoparticles as the Window Layer for CuIn(S,Se)2 Devices

As a wide‐bandgap semiconductor, titanium dioxide (TiO₂) with a porous structure has proven useful in dye‐sensitized solar cells, but its application in low‐cost, high‐efficiency inorganic photovoltaic devices based on materials such as Cu(InGa)Se₂ or Cu₂ZnSnS₄ is limited. Here, a thin film made from solution‐processed TiO₂ nanocrystals is demonstrated as an alternative to intrinsic zinc oxide (i‐ZnO) as the window layer of CuInS_xSe_1?x solar cells. The as‐synthesized, well‐dispersed, 6 nm TiO₂ nanocrystals are assembled into thin films with controllable thicknesses of 40, 80, and 160 nm. The TiO₂ nanocrystal films with thicknesses of 40 and 80 nm exhibit conversion efficiencies (6.2% and 6.33%, respectively) that are comparable to that of a layer of the typical sputtered i‐ZnO (6.42%). The conversion efficiency of the devices with a TiO₂ thickness of 160 nm decreases to 2.2%, owing to the large series resistance. A 9‐hour reaction time leads to aggregated nanoparticles with a much‐lower efficiency (2%) than that of the well‐dispersed TiO₂ nanoparticles prepared using a 15‐hour reaction time. Under optimized conditions, the champion TiO₂ nanocrystal‐film‐based device shows even higher efficiency (9.2%) than a control device employing a typical i‐ZnO film (8.6%).     

Deposition of iron titanate/titania ceramic composite thin films from a single molecular precursor

A heterobimetallic single molecular precursor, [Fe₂Ti₄(μ-O)₆(TFA)₈(THF)₆] (1) [TFA = trifluoroacetate, THF = tetrahydrofuran], was synthesized by the simple reaction of [Fe₃O(OAc)₆(H₂O)₃]NO₃·4H₂O [OAc = acetato] with tetrakis(2-ethoxyethanalato)titanium(IV) in the presence of trifluoroacetic acid in THF. The synthesized precursor was analyzed by melting point, CHN analysis, FTIR, single crystal X-ray diffraction and thermogravimetric analysis. Complex (1) crystallizes in the orthorhombic space group Pca2₁ with cell dimensions a = 19.2114(14), b = 20.4804(15) and c = 17.2504(12) Å, and the complex undergoes thermal decomposition at 490 °C to give a residual mass corresponding to an Fe₂TiO₅-TiO₂ composite mixture. The synthesized precursor was utilized for deposition of Fe₂TiO₅-TiO₂ composite thin films by aerosol-assisted chemical vapor deposition (AACVD) on glass substrates at 500 °C using argon as the carrier gas. Scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray powder diffraction (XRD) analyses of the thin films suggest the formation of good quality crystalline thin films of an Fe₂TiO₅-TiO₂ composite with an average grain size of 0.105-0.120 μm.     

Surface‐Plasmon Assisted Energy Conversion in Dye‐Sensitized Solar Cells

In this study, the effect of plasmonic core‐shell structures, consisting of dielectric cores and metallic nanoshells, on energy conversion in dye‐sensitized solar cells (DSSCs) is investigated. The structure of the core‐shell particles is controlled to couple with visible light so that the visible component of the solar spectrum is amplified near the core‐shell particles. In core‐shell particle – TiO₂ nanoparticle films, the local field intensity and light pathways are increased due to the surface plasmons and light scattering. This, in turn, enlarges the optical cross‐section of dye sensitizers coated onto the mixed films. When 22 vol% of core‐shell particles are added to a 5 μm thick TiO₂ film, the energy conversion efficiency of DSSCs increases from 2.7% to 4.0%, in spite of a more than 20% decrease in the amount of dyes adsorbed on the composite films. The correlation between core‐shell particle content and energy conversion efficiency in DSSCs is explained by the balance among near‐field effects, light scattering efficiency, and surface area in the composite films.     

A nanocomposite/crude extract enzyme-based xanthine biosensor

A novel amperometric biosensor for xanthine was developed based on covalent immobilization of crude xanthine oxidase (XOD) extracted from bovine milk onto a hybrid nanocomposite film via glutaraldehyde. Toward the preparation of the film, a stable colloids solution of core–shell Fe₃O₄/polyaniline nanoparticles (PANI/Fe₃O₄ NPs) was dispersed in solution containing chitosan (CHT) and H₂PtCl₆ and electrodeposited over the surface of a carbon paste electrode (CPE) in one step. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectrophotometry, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) were used for characterization of the electrode surface. The developed biosensor (XOD/CHT/Pt NPs/PANI/Fe₃O₄/CPE) was employed for determination of xanthine based on amperometric detection of hydrogen peroxide (H₂O₂) reduction at –0.35 V (vs. Ag/AgCl). The biosensor exhibited a fast response time to xanthine within 8 s and a linear working concentration range from 0.2 to 36.0 μM (R² = 0.997) with a detection limit of 0.1 μM (signal/noise [S/N] = 3). The sensitivity of the biosensor was 13.58 μA μM⁻¹ cm⁻². The apparent Michaelis–Menten (K_m) value for xanthine was found to be 4.7 μM. The fabricated biosensor was successfully applied for measurement of fish and chicken meat freshness, which was in agreement with the standard method at the 95% confidence level.     

Mesoporous TiO2 Beads Offer Improved Mass Transport for Cobalt‐Based Redox Couples Leading to High Efficiency Dye‐Sensitized Solar Cells

Overcoming ionic diffusion limitations is essential for the development of high‐efficiency dye‐sensitized solar cells based on cobalt redox mediators. Here, improved mass transport is reported for photoanodes composed of mesoporous TiO₂ beads of varying pore sizes and porosities in combination with the high extinction YD2‐o‐C8 porphyrin dye. Compared to a photoanode made of 20 nm‐sized TiO₂ particles, electrolyte diffusion through these films is greatly improved due to the large interstitial pores between the TiO₂ beads, resulting in up to 70% increase in diffusion‐limited current. Simultaneously, transient photocurrent measurements reveal no mass transport limitations for films of up to 10 μm thickness. In contrast, standard photoanodes made of 20 nm‐sized TiO₂ particles show non‐linear behavior in photocurrent under 1 sun illumination for a film thickness as low as 7 μm. By including a transparent thin mesoporous TiO₂ underlayer in order to reduce optical losses at the fluorine‐doped tin oxide (FTO)‐TiO₂ interface, an efficiency of 11.4% under AM1.5G 1 sun illumination is achieved. The combination of high surface area, strong scattering behavior, and high porosity makes these mesoporous TiO₂ beads particularly suitable for dye‐sensitized solar cells using bulky redox couples and/or viscous electrolytes.     

Bicarbonate use in three aquatic plants

Our study aimed to test the ability of aquatic plants to use bicarbonate when acclimated to three different bicarbonate concentrations. To this end, we performed experiments with the three species Ceratophyllum demersum, Egeria densa, Lagarosiphon major to determine photosynthetic rates under varying bicarbonate concentrations. We measured bicarbonate use efficiency, photosynthetic performance and respiration. For all species, our results revealed that photosynthetic rates were highest in replicates grown at low alkalinity. Thus, E. densa had approx. five times higher rates at low (264 ± 15 μmol O₂ g⁻¹ DW h⁻¹) than at high alkalinity (50 ± 27 μmol O₂ g⁻¹ DW h⁻¹), C. demersum had three times higher rates (336 ± 95 and 120 ± 31 μmol O₂ g⁻¹ DW h⁻¹), and L. major doubled its rates at low alkalinity (634 ± 114 and 322 ± 119 μmol O₂ g⁻¹ DW h⁻¹). Similar results were obtained for bicarbonate use efficiency by E. densa (136 ± 44 and 43 ± 10 μmol O₂ mequiv. L⁻¹ g⁻¹ DW h⁻¹) and L. major (244 ± 29 and 82 ± 24 μmol O₂ mequiv. L⁻¹ g⁻¹ DW h⁻¹). As to C. demersum, efficiency was high but unaffected by alkalinity, indicating high adaptation ability to varied alkalinities. A pH drift experiment supported these results. Overall, our results suggest that the three globally widespread worldwide species of our study adapt to low inorganic carbon availability by increasing their efficiency of bicarbonate use.     

Pharmacological evidence that Ca²+ channels and, to a lesser extent, K+ channels mediate the relaxation of testosterone in the canine basilar artery

Testosterone induces vasorelaxation through non-genomic mechanisms in several isolated blood vessels, but no study has reported its effects on the canine basilar artery, an important artery implicated in cerebral vasospasm. Hence, this study has investigated the mechanisms involved in testosterone-induced relaxation of the canine basilar artery. For this purpose, the vasorelaxant effects of testosterone were evaluated in KCl- and/or PGF_2α-precontracted arterial rings in vitro in the absence or presence of several antagonists/inhibitors/blockers; the effect of testosterone on the contractile responses to CaCl₂ was also determined. Testosterone (10-180 μM) produced concentration-dependent relaxations of KCl- or PGF_2α-precontracted arterial rings which were: (i) unaffected by flutamide (10 μM), dl-aminoglutethimide (10 μM), actinomycin D (10 μM), cycloheximide (10 μM), SQ 22,536 (100 μM) or ODQ (30 μM); and (ii) significantly attenuated by the blockers 4-aminopyridine (K_V; 1 mM), BaCl₂ (K_IR; 30 μM), iberiotoxin (BKCa2+; 20 nM), but not by glybenclamide (K_ATP; 10 μM). In addition, testosterone (31, 56 and 180 μM) and nifedipine (0.01-1 μM) produced a concentration-dependent blockade of the contraction to CaCl₂ (10 μM to 10 mM) in arterial rings depolarized by 60 mM KCl. These results, taken together, show that testosterone relaxes the canine basilar artery mainly by blockade of voltage-dependent Ca²⁺ channels and, to a lesser extent, by activation of K⁺ channels (K_IR, K_V and BKCa2+). This effect does not involve genomic mechanisms, production of cAMP/cGMP or the conversion of testosterone to 17β-estradiol.     

Interfacial electron transfer on TiO2 sensitized with an axially anchored trans tetradentate Ru(II) compound

The ruthenium complexes, trans-[Ru(phen-NH-phen)(eina)₂](PF₆)₂ and trans-[Ru(phen-NH-phen)(ina)₂](PF₆)₂ where phen-NH-phen = N,N-bis(1,10-phenanthroline-2-yl)amine, ina = isonicotinic acid and eina = ethyl isonicotinate, have been synthesized and characterized by ¹H NMR, elemental analysis, and IR spectroscopy. The compounds were non-emissive at room temperature, but displayed intense photoluminescence in 4:1 ethanol/methanol glasses at 77 K with corrected emission maximum at 570-580 nm. A quasi-reversible wave observed in cyclic voltammetry experiments was assigned to the Ru^III/II couple, E° (trans-[Ru(phen-NH-phen)(eina)₂)^3+/2+ = +1.22 V versus Ag/AgCl. The trans-[Ru(phen-NH-phen)(ina)₂](PF₆)₂ compound was found to bind to nanocrystalline TiO₂ thin films from acetonitrile solution. Pulsed 532 nm excitation of trans-[Ru(phen-NH-phen)(ina)₂](PF₆)₂ anchored to mesoporous nanocrystalline TiO₂ thin films resulted in an absorption difference spectra consistent with the formation of an interfacial charge separated state trans-[Ru^III (phen-NH-phen)(ina)₂]⁺/TiO₂ (e⁻). The formation of this state could not be time resolved, consistent with rapid excited state injection into the TiO₂, k_inj > 10⁸ s⁻¹. Comparative measurements with a thin film actinometer yielded an injection quantum yield (?_inj) of 0.8. Charge recombination required milliseconds for completion and followed a bi-second-order equal concentration kinetic model with k₁ = 1.0 × 10⁸ s⁻¹, and k₂ = 3.0 × 10⁵ s⁻¹. In regenerative solar cells with 0.5 M LiI and 0.005 M I₂ in acetonitrile, incident photon-to-current efficiencies were typically less than 10%.     

Rosiglitazone transiently disturbs calcium homeostasis in monocytic cells

The PPARγ agonist Rosiglitazone exerts anti-hyperglycaemic effects by regulating the long-term expression of genes involved in metabolism, differentiation and inflammation. In the present study, Rosiglitazone treatment rapidly inhibited (5-30 min) the ER Ca²⁺ ATPase SERCA2b in monocytic cells (IC₅₀ = 1.88 μM; p < 0.05), thereby disrupting short-term Ca²⁺ homeostasis (resting [Ca²⁺]_cyto = 121.2 ± 2.9% basal within 1 h; p < 0.05). However, extended Rosiglitazone treatment (72 h) induced dose-dependent SERCA2b up-regulation, and restored calcium homeostasis, in monocytic cells (SERCA2b mRNA: 138.7 ± 5.7% basal (1 μM)/215.0 ± 30.9% basal (10 μM); resting [Ca²⁺]_cyto = 97.3 ± 8.3% basal (10 μM)). As unfavourable cardiovascular outcomes, possibly related to disrupted cellular Ca²⁺ homeostasis, have been linked to Rosiglitazone, this effect may be of clinical interest. In contrast, in PPRE-luciferase reporter-gene assays, Rosiglitazone induced non-dose-dependent PPARγ-dependent effects (1 μM: 152.5 ± 4.9% basal; 10 μM: 136.1 ± 5.1% basal (p < 0.05 for 1 μM vs. 10 μM)). Thus, we conclude that Rosiglitazone can exert PPARγ-independent non-genomic effects, such as the SERCA2b inhibition seen here, but that long-term Rosiglitazone treatment did not perturb resting [Ca]_cyto in this study.     

The antioxidant effect of the mesoionic compound SYD-1 in mitochondria

The sydnone SYD-1 (3-[4-chloro-3-nitrophenyl]-1,2,3-oxadiazolium-5-olate] possesses important antitumor activity against Sarcoma 180 and Ehrlich tumors. We previously showed that SYD-1 depresses mitochondrial phosphorylation efficiency, which could be involved in its antitumoral activity. Considering the important role of mitochondria in the generation of reactive oxygen species (ROS) and the involvement of ROS in cell death mechanisms, we evaluated the effects of SYD-1 on oxidative stress parameters in rat liver mitochondria. SYD-1 (0.5 and 0.75 μmol mg⁻¹ protein) inhibited the lipoperoxidation induced by Fe³⁺/ADP-oxoglutarate by approximately 75% and promoted total inhibition at the highest concentration tested (1.0 μmol mg⁻¹ protein). However, SYD-1 did not affect lipoperoxidation started by peroxyl radicals generated by α-α′-azodiisobutyramidine dihydrochloride. The mesoionic compound (0.25–1.0 μmol mg⁻¹ protein) demonstrated an ability to scavenge superoxide radicals, decreasing their levels by 9–19%. The activities of catalase and superoxide dismutase did not change in the presence of SYD-1 (0.25–1.0 μmol mg⁻¹ protein). SYD-1 inhibited mitochondrial swelling dependent on the formation/opening of the permeability transition pore induced by Ca²⁺/phosphate by approximately 30% (1.0 μmol mg⁻¹ protein). When Ca²⁺/H₂O₂ were used as inducers, SYD-1 inhibited swelling only by approximately 12% at the same concentration. NADPH oxidation was also inhibited by SYD-1 (1.0 μmol mg⁻¹ of protein) by approximately 48%. These results show that SYD-1 is able to prevent oxidative stress in isolated mitochondria and suggest that the antitumoral activity of SYD-1 is not mediated by the increasing generation of ROS.     

Deposition and characterization of ZnO thin films from a novel hexanuclear zinc precursor

The high nuclearity zinc complex, Zn₆(OAc)₈(μ-OH)₂(dmae)₂(dmaeH)₂ (1) (OAc = acetate and dmaeH = N,N′-dimethylaminoethanol), having a low decomposition temperature and sufficiently high solubility in non-polar solvents, was synthesized by a simple chemical technique in high yield and analyzed by melting point, elemental analysis, FTIR, NMR, single crystal X-ray crystallography and thermal analysis. Aerosol-assisted chemical vapor deposition technique was used to deposit a high-quality thin film with good adhesion to the glass substrate at relatively low temperature (320 °C). Scanning electron microscopy of the film shows clearly distinct crystallites of uniform shape with 2.4-2.9 μm size. Powder X-ray diffraction measurements have indicated the deposition of a crystalline phase of hexagonal ZnO with space group P63mc.     

Artificial photosynthesis based on dye-sensitized nanocrystalline TiO2 solar cells

A new series of amphiphilic heteroleptic ruthenium(II) sensitizers [Ru(H₂dcbpy)(dhbpy)(NCS)₂] (C1), [Ru(H₂dcbpy)(bccbpy)(NCS)₂] (C2), [Ru(H₂dcbpy)(mpubpy)(NCS)₂] (C3), [Ru(H₂dcbpy)(bhcbpy)(NCS)₂] (C4) have been synthesized and fully characterized by UV-Vis, emission, NMR and cyclic voltammetric studies (where dhbpy = 4,4′-dihexyl-2,2′-bipyridine, bccbpy = 4,4′-bis(cholesteroxycarbonyl)-2,2′-bipyridine, mpubpy = 4-methyl-4′-perfluoro-1H,1H,2H,2H,3H,3H-undecyl-2,2′-bipyridine, bhcbpy = 4,4′-Bis(hexylcarboxamido)-2,2′-bipyridine). The amphiphilic amide heteroleptic ruthenium(II) sensitizers, self-assembled on TiO₂ surface from ethanol solution, reveal efficient sensitization in the visible window range yielding ≈80% incident photon-to-current efficiencies (IPCE). Under standard AM 1.5 sunlight, the C4 sensitizer gave 15 mA/cm² short circuit photocurrent density, 0.66 fill factor and an open circuit voltage of 0.75 V, corresponding to an overall conversion efficiency of 7.4%.