Dye-Sensitized Solar Cells with a High Absorptivity Ruthenium Sensitizer Featuring a 2-(Hexylthio)thiophene Conjugated Bipyridine

We conjugated 2-(hexylthio)thiophene with bipyridine to construct a new heteroleptic polypyridyl ruthenium sensitizer exhibiting a charge-transfer band at 550 nm with a molar extinction coefficient of 18.7 x 10(3) M-1 cm(-1). In contrast to its analogues Z907 and C101, a mesoporous titania film stained with this new sensitizer featured a short light absorption length, allowing for the use of a thin photoactive layer for efficient light-harvesting and conversion of solar energy to electricity. With a preliminary testing, we have reached 11.4% overall power conversion efficiency measured at the air mass 1.5 global conditions. Transient photoelectrical decays and electrical impedance spectra were analyzed to picture the intrinsic physics of temperature-dependent photovoltage and photocurrent.

Free-Radical Solution Copolymerization of the Ionic Liquid Monomer 1-Vinyl-3-Ethylimidazolium Bromide with Acrylonitrile

Ionic liquid monomer 1-vinyl-3-ethylimidazolium bromide (ViEtIM(+)Br(-)) was first used to copolymerize with acrylonitrile (AN) successfully under various conditions. This was achieved with azobisisobutyronitrile as the initiator and dimethyl sulfoxide as the solvent. The kinetics of this copolymerization were studied. The values of the monomer apparent reactivity ratios were calculated by the Kelen-Tudos method. The apparent reactivity ratios of ViEtIM(+)Br(-) (r(ViEtIM+Br-)) and AN (r(AN)) were similar at polymerization conversions of less than 10%, (r(AN) = 0.954, r(ViEtIM+Br-) = 0.976). The copolymers were obtained with high molecular weights and high hydrophilicides. The copolymers were characterized by H-1-NMR, differential scanning calorimetry, and thermogravimetric analysis. These copolymers may be potentially useful in the preparation of precursor fibers and carbon fibers.

A Novel Strategy to Branched Polyacrylonitrile Via One-Pot RAFT Copolymerization of Acrylonitrile and an Asymmetrical Divinyl Monomer

Branched polyacrylonitriles were prepared via the one-pot radical copolymerization of acrylonitirle and an asymmetric divinyl monomer (allyl methacrylate) that possesses both a higher reactive methacrylate and a lower reactive allyl. RAFT technique was used to keep a low-propagation chain concentration via a fast reversible chain transfer euilibration and thus the cross-linking was prevented until a high level of monomer conversions. This novel strategy was demonstrated to engenerate a branched architecture with abundant pendant functional vinyl and nitrile groups, and controlled molecular weight as a behavior of controlled/living radical polymerization characteristics. The effect of the various experimental parameters, including temperature, brancher to monomer molar ratio, and chain transfer agent to initiator molar ratio, on the control Of moleculer dimension (molecular weight and polydispersity indices) and the degree of branching were investigated in detail. Moreover, H-1 NMR and gel permeation chromatography confirm the branched architecture of the resultant polymer. The intrinsic viscosity of the copolymer is also lower than the linear counterpart.

[Ru(bpy)(2)(dcbpy)NHS] Labeling/Aptamer-Based Biosensor for the Detection of Lysozyme by Increasing Sensitivity with Gold Nanoparticle Amplification

A novel [Ru(bpy)(2) (dcbpy)NHS] labeling/aptamer-based biosensor combined with gold nanoparticle amplification for the determination of lysozyme with an electrochemiluminescence (ECL) method is presented. In this work, an aptamer, an ECL probe, gold nanoparticle amplification, and competition assay are the main protocols employed in ECL detection. With all the protocols used, an original biosensor coupled with an aptamer and [Ru(bpy)(2)(dcbpy)NHS] has been prepared. Its high selectivity and sensitivity are the main advantages over other traditional [Ru(bpy)(3)](2+) biosensors. The electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM) characterization illustrate that this biosensor is fabricated successfully. Finally, the biosensor was applied to a displacement assay in different concentrations of lysozyme solution, and an ultrasensitive ECL signal was obtained. The ECL intensity decreased proportionally to the lysozyme concentration over the range 1.0 x 10-(13)-1.0 x 10(-8) mol L-1 with a detection limit of 1.0 x 10(-13) mol L-1.

Lung alveolar proteomics of bronchoalveolar lavage from a pulmonary alveolar proteinosis patient using high-resolution FTICR mass spectrometry

High-resolution Fourier transform ion cyclotron resonance (FTICR) mass spectrometry was developed and applied to the proteome analysis of bronchoalveolar lavage fluid (BALF) from a patient with pulmonary alveolar proteinosis. With use of 1-D and 2-D gel electrophoresis, surfactant protein A (SP-A) and other surfactant-related lung alveolar proteins were efficiently separated and identified by matrix-assisted laser desorption/ionization FTICR mass spectrometry . Low molecular mass BALF proteins were separated using a gradient 2-D gel. An efficient extraction/precipitation system was developed and used for the enrichment of surfactant proteins. The result of the BALF proteome analysis show the presence of several isoforms of SP-A, in which an N-non-glycosylierte form and several proline hydroxylations were identified. Furthermore, a number of protein spots were found to contain a mixture of proteins unresolved by 2-D gel electrophoresis, illustrating the feasibility of high-resolution mass spectrometry to provide identifications of proteins that remain unseparated in 2-D gels even upon extended pH gradients.

Studies on the doubly charged cluster ions of sodium and potassium nitrates by electrospray ionization tandem mass spectrometry

Doubly charged cluster ions, besides singly charged cluster ions, from sodium and potassium nitrates were produced evidently under normal source capillary temperature of 200 degrees C in both positive and negative ion electrospray ionization (ESI) ion trap mass spectrometry. The fragmentation pathways for doubly charged cluster ions were studied in detail using ESI tandem mass spectrometry and two pathways were observed depending on the cluster sizes of alkali metal nitrates. In addition, factors that affect the formation of cluster ions were also interrogated.

Control led/living free-radical copolymerization of 4-(azidocarbonyl) phenyl methacrylate with methyl acrylate under Co-60 gamma-ray irradiation

A new vinyl acyl azide monomer, 4-(azidocarbonyl) phenyl methacrylate, has been synthesized and characterized by NMR and FTIR spectroscopy. The thermal stability of the new monomer has been investigated with FTIR and thermal gravimetry/differential thermal analysis (TG/DTA), and the monomer has been demonstrated to be stable below 50 degrees C in the solid state. The copolymerizations of the new monomer with methyl acrylate have been carried out at room temperature under Co-60 gamma-ray irradiation in the presence of benzyl 1-H-imidazole-1-carbodithioate. The results show that the polymerizations bear all the characteristics of controlled/living free-radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow (< 1.20), and a linear relationship existing between In([M](0)/[M]) and the polymerization time. The data from H-1 NMR and FTIR confirm that no change in the acyl azide groups has occurred in the polymerization process and that acyl azide copolymers have been obtained. The thermal stability of the polymers has also been investigated with TG/DTA and FTIR.

Spectrophotometric determination of water content in alcohol organic solvents

In this work, the absorption spectral characteristics and color-change reaction mechanism of cobalt(II) chloride(COCl2) in alcohol organic solvents has been investigated in the presence of water, and then the optimum conditions for determining the water content in the solvents were selected. Results indicated that the absorption spectra Of COCl2 in alcohols decreased with the increment of water content. At the maximum absorption wavelength of 656 nm, there were good linear relationships between the logarithm of the absorbance and the water content in organic solvents such as ethanol, n-propanol, iso-propanol and n-butanol with related coefficients in the range of 0.9996 similar to 0.9998. For determining water content in organic solvents, this method is simple, rapid, sensitive, reproducible and environmentally friendly. Furthermore, the linear range cannot restrict determination of the water content in organic solvents. This method had been applied to determine the water content in ethanol and n-butanol with satisfactory recovery of water in n-butanol between 98.41%-101.29%.

Synthesis of AgCl/PAN composite nanofibres using an electrospinning method

A new route based on electrospinning is designed for the preparation of silver chloride/polyacrylonitrile (AgCl/PAN) composite nanofibres. The AgCl nanoparticles uniform in size, were dispersed on the surfaces of the composite nanofibres. Transmission electron microscopy (TEM) images gave direct evidence of the structure. X-ray photoelectron spectroscopy (XPS) and x-ray diffraction (XRD) confirmed the presence of AgCl crystals.

A simple and effective route for the preparation of poly(vinylalcohol) (PVA) nanofibers containing gold nanoparticles by electrospinning method

Poly(vinyl alcohol) (PVA) nanofibers containing gold nanoparticles have been simply obtained by electrospinning a solution containing gold nanoparticles without the additional step of introducing other stabilizing agents. The optical property of gold nanoparticles in PVA aqueous solution was observed by UV-visible absorption spectra. Morphology of the Au/PVA nanofibers and distribution of the gold nanoparticles were characterized by transmission electron. microscopy (TEM). The structure transformation was characterized from PVA to PVA/Au composite by Fourier transform infrared spectroscopy (FTIR).

Characterization of the rutin-metal complex by electrospray ionization tandem mass spectrometry

According to the strong application background of bioflavonoid and metal-flavonoid complexes, novel electrospray ionization tandem mass spectrometry (ESI-MSn) was applied to investigate the structure and fragmentation mechanism of transition metal-rutin complexes. In the full-scan mass spectra, different stoichiometric ratios of rutin-metal complexes were found. In the reaction between rutin and Cu, four kinds of complexes with four different stoichiometric ratios were produced. In the reaction between rutin and Zn, Mn(II), and Fe(II), only two kind of complexes with stoichiometric ratios of 1:1 and 1:2 occured. In further tandem mass spectrometric experiments of different rutin-metal complexes, product fragments, came from the neutral loss of the external rhamnose and the internal glucose unit, oligosaccharide chain, aglycone, and small organic molecules. According to the MSn data, we proposed a mechanism for all fragments of the rutin-Cu complex A and the structure of two rutin-Cu complexes, C and D.

In situ circular dichroic electrochemical study of bilirubin and bovine serum albumin complex

The electrooxidation of bilirubin (BR) and bovine serum albumin (BSA) complexes was studied by in situ circular dichroism (CD) spectroelectrochemistry. The result showed that the mechanism of the whole electrooxidation process of this complex corresponded to electrochemical processes (EE mechanism) in aqueous solution. Some parameters of the process were obtained by double logarithm method, differential method and nonlinear regression method. In visible region, CD spectra of the two enantiomeric components of the complex and their fraction distribution against applied potentials were obtained by singular value decomposition least-square (SVDLS) method. Meanwhile, the distribution of the five components of secondary structure was also obtained by the same method in far-UV region. The peak potential gotten from EE mechanism corresponds to a turning point for the component transition, beyond which the whole reaction reaches a new equilibrium. Under applied positive potentials, the enantiomeric equilibrium between M and P form is broken and M form transfers to its enantiomer of P, while the fraction of alpha-helix increases and that improves the transition to P form.

Synthesis of new bis-BINOLs linked by a 2,2 '-bipyridine bridge

A series of new G-symmetric chiral ligands 8, 9, 11 and 12, consisting of two binaphthyl units linked by a 2,2'-bipyridine bridge, has been synthesized via Suzuki cross-coupling reactions.

Sol-ogel deposition and luminescence properties of lanthanide ion-doped Y2(1-x)Gd2xSiWO8 (0 <= x <= 1) phosphor films

Y2(1-x) Gd2xSiWO8 : A ( 0 <= x <= 1; A= Eu3+, Dy3+, Sm3+, Er3+) phosphor films have been prepared on silica glass substrates through the sol - gel dip-coating process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), atomic force microscope (AFM), scanning electron microscopy (SEM) and photoluminescence spectra as well as lifetimes were used to characterize the resulting films. The results of the XRD indicated that the films began to crystallize at 800 degrees C and crystallized completely at 1000 degrees C. The AFM and SEM study revealed that the phosphor films, which mainly consisted of closely packed grains with an average size of 90 - 120 nm with a thickness of 660 nm, were uniform and crack free. Owing to an efficient energy transfer from the WO42- groups to the activators, the doped lanthanide ion ( A) showed its characteristic f - f transition emissions in crystalline Y2(1-x) Gd2xSiWO8 (0 <= x <= 1) films. The optimum concentrations for Eu3+, Dy3+, Sm3+, Er3+ were determined to be 21, 5, 3 and 7 mol% of Y3+ in Y2SiWO8 films, respectively.