A 2-quinolinecarboxylate-substituted ruthenium(II) complex as a new type of sensitizer for dye-sensitized solar cells

A new type of ruthenium(II) complex containing a 2-quinolinecarboxylate ligand was designed and synthesized as a sensitizer for dye-sensitized solar cells, and its photophysical and photochemical properties were characterized. The solar cells created with this complex exhibited efficient panchromatic sensitization over the entire visible wavelength range extending into the near-IR region. An overall conversion efficiency of 8.2% was attained under standard air mass 1.5 irradiation (100 mW cm⁻²) with the short-circuit photocurrent density of 18.2 mA cm⁻², the open-circuit photovoltage of 0.63 V and the fill factor of 0.72.     

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%.     

An alternative ionic liquid based electrolyte for dye-sensitized solar cells.

An ionic liquid based, environmentally friendly electrolyte LiI(C(2)H(5)OH)(4)-I(2) was used as the electrolyte to fabricate dye-sensitized solar cells (DSSC) with energy conversion efficiency of 4.9% under AM 1.5 (100 mW cm(-2)) irradiation.     

Dye-sensitized solar cells based on PEDOP as a hole conductive medium

Dye-sensitized photo-electrochemical cells based on a solid poly-(3,4-(ethylenedioxy)pyrrole) (PEDOP) electron mediating matrix were assembled and photo-electrochemically characterized. The conductive polymer was directly grown on the sensitized TiO₂ surface exploiting a photo-assisted electropolymerization promoted by a properly designed ruthenium dye bearing pyrrole functionalities. J-V characteristics and photoaction spectra indicated very low efficiencies mainly determined by an efficient recombination of photo-injected electrons with both PEDOP acceptor states and oxidized sensitizers.     

Theoretical design of organic-inorganic hybrids based on hexamolybdate toward high performance dye-sensitized solar cells

The electronic structures, absorption spectra and photovoltaic (PV) performance of four dyes based on triphenylamine and polyoxometalate (POM) organic–inorganic hybrids for p-type dye-sensitised solar cells have been discussed by density functional theory (DFT) and time-dependent DFT calculations. In the four designed dyes, the triarylamine and carbazole take the role of the electron donor and the POMs act as the electron acceptor. It was found that introduction of electron donating groups (diphenylamine group and carbazole) into the triarylamine unit enabled better PV performance. This work is expected to be helpful for designing triarylamine–POM hybrid dyes with target properties.     

Rapid synthesis of bis (2,2′-bipyridine) nitratocopper(II) nitrate using a hydrothermal method and its application to dye-sensitized solar cells

In this study we synthesized bis (2,2′-bipyridine) nitratocopper(II) nitrate in order to examine its the crystal structure, optical property and application to dye-sensitized solar cells (DSSCs). Single X-ray analysis results revealed that the acquired complex exhibited five-coordination with four nitrogen atoms of bipyridine and the oxygen bond of the ion. The reflectance UV-Vis absorptions showed three absorptions that were assigned to ligand-to-ligand at around 230-350 nm, metal-to-ligand charge transfer at around 350-600 nm, and d-d transfer at around ∼650 nm. Cyclic voltammetry in acetonitrile revealed a reversible Cu(I) → Cu(II) oxidation process at a highest occupied molecular orbital (HOMO) and a lowest unoccupied molecular orbital (LUMO) levels of −4.692 and −4.071 eV, respectively. The photoelectric efficiency in DSSCs was approximately 0.032% with the nanometer-sized TiO₂ in the condition of an open-circuit voltage (V_oc) of 0.346 V, a short-circuit current density (J_sc) of 0.166 mA/cm² at an incident light intensity of 100 mW/cm².     

Label-free detection of DNA hybridization based on a novel functionalized conducting polymer

A new functionalized pyrrole monomer, 3-pyrrolylacrylic acid (PAA) was synthesized. It was used to prepare a copolymer with pyrrole, poly(Py-co-PAA), which was investigated by reflective FT-IR, UV-vis spectroscopy and cyclic voltammetry. A label-free DNA sensor was prepared based on a poly(Py-co-PAA) film. Hybridization with complementary and non-complementary DNA targets was studied by electrochemical impedance spectroscopy. Results show a significant increase in the charge-transfer resistance upon addition of complementary target. The impedance spectra were analyzed by using a modified Randles and Ershler equivalent circuit model. The change in charge-transfer resistance that was used as an index of sensor response was found to be linear with logarithmic target concentration in the range of 2 x 10(-9) to 2 x 10(-7)M. The detection limit was 0.98 nM.     

A glucose biosensor based on TiO(2)-Graphene composite

A novel glucose biosensor was developed based on the adsorption of glucose oxidase at a TiO(2)-Graphene (GR) nanocomposite electrode. A TiO(2)-GR composite was synthesized from a colloidal mixture of TiO(2) nanparticles and graphene oxide (GO) nanosheets by an aerosol assisted self-assembly (AASA). The particle morphology of all TiO(2)-GR composites was spherical in shape. It was observed that micron-sized TiO(2) particles were encapsulated by GR nanosheets and that the degree of encapsulation was proportional to the ratio of GO/TiO(2). The amperometric response of the glucose biosensor fabricated by the TiO(2)-GR composite was linear against a concentration of glucose ranging from 0 to 8mM at -0.6V. The highest sensitivity was noted at about 6.2μA/mMcm(2). The as prepared glucose biosensor based on the TiO(2)-GR composite showed higher catalytic performance for glucose redox than a pure TiO(2) and GR biosensor.     

Visible light decomposition of ammonia to N2 with Ru(bpy)3(2+) sensitizer.

Visible light decomposition of aqueous NH3 to N2 was investigated using a photocatalyst aqueous solution based on molecular photoelectron relay systems of either sensitizer (tris(2,2'-bipyridine)ruthenium(II), (Ru(bpy)3(2+))/potassium peroxodisulfate(K(2)S(2)O(8)) or Ru(bpy)3(2+)/methylviologen dichloride(MV2+)/O2, capable of using visible light instead of UV-driven semiconductors such as TiO2. It was confirmed by using an in situ visible absorption spectral change under irradiation that the Ru(II) complex is oxidized to the Ru(III) complex by K(2)S(2)O(8), and that the Ru(III) complex formed is stable without NH3, while the added NH3 was oxidized by the Ru(III) complex to produce the Ru(II) complex. In the presence of 1 mM NH3 aqueous solution, the Ru(III) complex was the predominant species under the photostationary state, but in the presence of 100 mM NH3, Ru(II) predominated. Gas-chromatographic analysis of the gaseous phase in the presence of 8.1 M NH3 showed that the photochemical oxidation of ammonia yielded N2. It was also demonstrated by using the in situ visible absorption spectrum under irradiation of the NH3 (1 M)/Ru(bpy)3(2+) (0.1 mM)/MV2+ (10 mM) system under Ar that MV+* is accumulated, showing that NH3 works as an electron donor for MV+* accumulation with simultaneous formation of the oxidized product of ammonia ((NH3)ox) without producing N2. It was suggested that the reduced product (MV+*) and the oxidized product ((NH3)ox) are in a kind of dynamic equilibrium prohibiting further oxidation of (NH3)ox by Ru(bpy)3(3+) to N2. In the O2 atmosphere, the oxidation of MV+* to MV2+ takes place to accumulate Ru(III) complex, so that (NH3)ox was further oxidized to N2. The high activity of IrO2 as a cocatalyst in this system was demonstrated.     

A highly sensitive, label-free gene sensor based on a single conducting polymer nanowire

A prerequisite for exploiting sensing devices based on semiconductor nanowires is ultra-sensitive and selective direct electrical detection of biological and chemical species. Here, we constructed a transducer based on copolymer of poly(3,4,-ethylenedioxythiophene) (PEDOT) and carboxylic group functionalised PEDOT single nanowire in between gold electrodes, followed by covalent attachment of amino-modified probe oligonucleotide. The target ODNs specific to Homo sapiens Breast and ovarian cancer cells were detected at femtomolar concentration and incorporation of negative controls (non-complementary ODN) were clearly discriminated by the sensor. The ex situ measurements were performed by using two terminal device setup and the changes in the interface of the nanowire associated with the association or dissociation of ODNs were measured as change in resistance. In addition, in situ measurements were performed by utilizing scanning ion conductance microscopy to measure the change in resistance of probe modified nanowire upon addition of different concentration of target ODNs in presence of relevant buffer. The constructed, nano sensor showed highly sensitive concentration dependent resistance change.     

A lactate biosensor based on lactate dehydrogenase/nictotinamide adenine dinucleotide (oxidized form) immobilized on a conducting polymer/multiwall carbon nanotube composite film

An amperometric lactate biosensor was developed based on a conducting polymer, poly-5,2′-5′,2′′-terthiophene-3′-carboxylic acid (pTTCA), and multiwall carbon nanotube (MWNT) composite on a gold electrode. Lactate dehydrogenase (LDH) and the oxidized form of nicotinamide adenine dinucleotide (NAD⁺) were subsequently immobilized onto the pTTCA/MWNT composite film. The modified electrode was characterized by quartz crystal microbalance (QCM), scanning electron microscopy (SEM), and electrochemical experiments. The detection signal was amplified by the pTTCA/MWNT assembly onto which a sufficient amount of enzyme was immobilized and stabilized by the covalent bond formation between the amine groups of enzyme and the carboxylic acid groups of the pTTCA/MWNT film. Experimental parameters affecting the sensor responses, such as applied potential, pH, and temperature, were assessed and optimized. Analytical performances and dynamic ranges of the sensor were determined, and the results showed that the sensitivity, stability, and reproducibility of the sensor improved significantly using pTTCA/MWNT composite film. The calibration plot was linear (r² = 0.9995) over the range of 5 to 90 μM. The sensitivity was approximately 0.0106 μA/μM, with a detection limit of 1 μM, based on a signal/noise ratio of 3. The applicability of the sensor for the analysis of l-lactate concentration in commercial milk and human serum samples was demonstrated successfully.     

Cyclometalated iridium(iii)-sensitized titanium dioxide solar cells.

Ir(iii) dyes used as sensitizers in dye-sensitized solar cells produced quantum yields approaching unity for conversion of absorbed photons to current under simulated air mass 1.0 sunlight, with current production resulting from ligand-to-ligand charge-transfer states, rather than the typical metal-to-ligand charge-transfer states in ruthenium-based cells.     

Influence of incubation time and sensitizer localization on meta-tetra(hydroxyphenyl)chlorin (mTHPC)-induced photoinactivation of cells

The present study addresses the impact of different aggregation states of meta-tetra(hydroxyphenyl)chlorin (mTHPC) on the photoinactivation of cells. Measurements of the photophysical properties of mTHPC in MCF-7 cells showed progressive sensitizer aggregation with increasing incubation time. Reconstructed absorption spectra of intracellular mTHPC showed a significant decrease in the molar extinction coefficient and broadening of the Soret band at 24 h incubation compared to 3 h. Intracellular photobleaching of mTHPC slowed down, and the profile changed from mono- to bi-exponential upon incubation. Fluorescence lifetime imaging (FLIM) measurements revealed a substantial decrease in the lifetime of mTHPC fluorescence at 24 h compared to 3 h. In addition, the intracellular localization of mTHPC as observed by fluorescence microscopy changed from a diffuse homogeneous fluorescence pattern at short incubation times to a punctiform pattern at 24 h. The efficiency of photodynamic therapy (PDT) assessed by a clonogenic assay was three times greater at 24 h. However, when the survival curves were replotted as a function of the number of absorbed photons, the efficiency was 1.8 times greater at 3 h than at 24 h. The loss of photosensitizing efficiency at higher mTHPC concentrations was attributed to self-quenching of the triplet states of the sensitizers.     

Photo-induced H2 production by [NiFe]-hydrogenase from T. roseopersicina covalently linked to a Ru(II) photosensitizer

The potential of hydrogen as a clean renewable fuel source and the finite reserves of platinum metal to be utilized in hydrogen production catalysts have provided the motivation for the development of non-noble metal-based solutions for catalytic hydrogen production. There are a number of microorganisms that possess highly efficient hydrogen production catalysts termed hydrogenases that generate hydrogen under certain metabolic conditions. Although hydrogenases occur in photosynthetic microorganisms, the oxygen sensitivity of these enzymes represents a significant barrier in directly coupling hydrogen production to oxygenic photosynthesis. To overcome this barrier, there has been considerable interest in identifying or engineering oxygen tolerant hydrogenases or generating mimetic systems that do not rely on oxygen producing photocatalysts. In this work, we demonstrate photo-induced hydrogen production from a stable [NiFe]-hydrogenase coupled to a [Ru(2,2'-bipyridine)₂(5-amino-1,10-phenanthroline)]²⁺ photocatalyst. When the Ru(II) complex is covalently attached to the hydrogenase, photocatalytic hydrogen production occurs more efficiently in the presence of a redox mediator than if the Ru(II) complex is simply present in solution. Furthermore, sustained hydrogen production occurs even in the presence of oxygen by presumably creating a local anoxic environment through the reduction of oxygen similar to what is proposed for oxygen tolerant hydrogenases. These results provide a strong proof of concept for engineering photocatalytic hydrogen production in the presence of oxygen using biohybrid mimetic systems.     

Near-infrared luminescent lanthanide (Er, Nd) complexes covalently bonded to a terpyridine-functionalized silica matrix.

New kinds of hybrid materials containing covalently bonded tris(dibenzoylmethanate)Ln complexes (Ln=Er, Nd) in a terpyridine-functionalized silica matrix have been prepared and their near-infrared luminescence properties reported.     

Selective isolation of endo-D-galacturonanase of Aspergillus niger based on interaction with tri(D-galactosiduronic acid) covalently bound to poly(hydroxyalkyl methacrylate)

A selective affinity-adsorbent for the extracellular endo-D-galacturonanase (E.C. 3.2.1.15) of Aspergillus niger was prepared by covalent coupling of tri(D-galactosiduronic acid) to Separon, a poly(hydroxyalkyl methacrylate) gel. Complexing of the enzyme with the adsorbent is pH dependent; maximal interaction occurs at the optimum pH for enzyme activity. The enzyme was quantitatively displaced from the adsorbent either by changing the pH or by bioelution with soluble tri(D-galactosiduronic acid) or other substrate. Within the range of substitution of Separon examined [content of tri(D-galactosiduronic acid) 1.7-6.7%] the amount of endo-D-galacturonanase retained was proportional to the content of affinity ligand. Under the same conditions, unsubstituted carrier did not complex with endo-D-galacturonanase. The dissociation constant of the affinity complex, as determined by zonal analysis, kinetic measurements, and by means of the adsorption isotherm KL (0.54 mmol.L-1), is close to the value (KI 0.44 mmol.L-1) obtained by the two first methods with soluble tri(D-galactosiduronic acid). The results show that adsorption of endo-D-galacturonanase on tri(D-galactosiduronic acid)-Separon is due exclusively to active-site-directed interaction with bound affinity-ligand.     

Electroreduction of O(2) to water at 0.6 V (SHE) at pH 7 on the "wired" Pleurotus ostreatus laccase cathode

O(2) was electroreduced to water at 0.6 V (SHE) near neutral pH on the "wired" Pleurotus ostreatus laccase cathode. We previously reported high-current density (5 mA cm(-2)), four-electron electroreduction of O(2) to water on a "wired" Coriolus hirsutus laccase electrode at +0.7 V (SHE) in pH 5 in citrate buffer. Since the enzyme was inhibited by chloride and because its activity declined steeply when the pH was raised to neutral, the rate of O(2) electroreduction in a physiological buffer solution was only approximately 1% of that at pH 5 in absence of chloride. Here we show that substitution of the C. hirsutus laccase by laccase from P. ostreatus allows the upward extension of the pH range of O(2) electroreduction. The current density of the electrode made with laccase from P. ostreatus in pH 7 citrate buffer was approximately 100 microA cm(-2) and at pH 7 and in phosphate buffered NaCl (PBS, 20 mM phosphate, 0.1 M NaCl) it still retained 6% of its maximal (1 mA cm(-2)) current density at pH 5 in citrate buffer. The electrocatalyst consisted of the crosslinked P. ostreatus laccase and the electron conducting redox polymer PVI-Os(dmebpy)(tpy)(2+/3+) [PVI=poly(N-vinyl imidazole) with about 1/5th of the rings complexed with (Os-dmebpy-tpy)(2+/3+); dmebpy=4,4'-dimethyl-2,2'-bipyridine; tpy=2,2',6',2"-terpyridine].