Investigation of the stability of solid-state dye-sensitized solar cells

The stability of the TiO₂/ruthenium dye/CuI solid-state solar cell was investigated under continuous simulated sunlight illumination. The cells showed fast degradation under full-spectrum sunlight illumination, but showed rather good stability when the ultraviolet part of the illumination was removed. XPS measurements showed evidence that TiO₂ could oxidize CuI in the presence of UV light. The photo-degradation mechanism of the cells is thus discussed on the basis of the photo-oxidative function of TiO₂. The long-term stability of the solid-state dye-sensitized solar cell (DSSC) was found to be improved under simulated sunlight by coating the TiO₂ porous electrode with an ultra-thin MgO layer, which was able to block the photo-oxidative activity of the TiO₂.     

Crystal and solution structures of photochromic spirobenzothiopyran. First full characterization of the meta-stable colored species.

Full elucidation for stable, colorless, and meta-stable colored structures of a new spirobenzothiopyran has been achieved both in the solid state and in a solution. 1',3',3'-Trimethyl-6-nitrospiro[(2H)-1-benzothiopyran-2,2'-indoline] with an ester group as a substituent at the 8-position of 1-sp shows photochromism. The blue-green colored species resulted from UV irradiation (365 nm) in one minute and spontaneously bleaches within one minute in acetone and methanol at 27 degrees C. UV exposure (365 nm) of 1-sp in methanol for 3 h at room temperature results in the growth of deep blue needlelike single crystals of the open form of spirobenzothiopyran, photomerocyanine 1-pmc, whose structures in the solid state and in solution were obtained unambiguously. The X-ray structural analysis of 1-pmc revealed the molecular structure of the zwitterionic photomerocyanine with s-trans,s-trans conformation. 1-pmc is soluble to polar solvents and thermally returns to 1-sp. In the DMSO solution, 1-pmc is found to return slowly to 1-sp (1-pmc gave only 18% of 1-sp for 30 min at 22 degrees C). The detailed NMR studies in DMSO-d(6) including COSY and NOE techniques as well as isotope labeling of the compound showed the structure with s-trans,s-cis conformation in a solution.     

Circular dichroism of copoly(γ-stearyl-L-glutamate–γ-methyl-L-glutamate)

Copoly(γ-stearly-L -glutamate-γ-methyl-L -glutamate)s with various compositions were synthesized by the ester exchange reaction of poly(γ-methyl-L -glutamate). Circular dichroism studies were carried out for solution and solid film as a function of the degree of stearylation and temperature. The slight and gradual temperature dependence of molecular ellipticity was observed for solution of all the copolyglutamates studied here and for the solid film of the copolyglutamate with the degree of stearylation of 16%, indicative of no reversal in the helix sense. However the remarkable change in negative molecular ellipticity with temperature was detected for the solid film of the copolyglutamate with a low degree of stearylation, e.g., 52%, whereas the drastic change in molecular ellipticity from a negative to positive value appeared for that with a higher degree of stearylation. This is discussed in terms of the reversal in the helix sense from a right- to left-handed α helix with the increase of temperature occurring at the melting temperature of the ordered side chain region.     

Flexible polyaniline

Flexible polyaniline having excellent mechanical properties (e.g., elongation at break = 41% and tensile strength = 1.8 kg cm^?2) was prepared by electrochemical reduction of ordinary polyaniline in organic solvents. The flexibility is directly related with the polymer morphology which was definitely affected by the nature of electrolyte anion. Perchlorate or tetrafluoroborate anion were found suitable to obtain flexible polyaniline. At the same time, it is essential that the polymer so prepared should be reduced (undoped) in some suitable organic solvents before making a flexible free standing film.     

On the problem of potential shifts at glassy carbon electrodes: Part II. Voltammetric analysis of the surface interactions involved in the electrode processes of nitrobenzenes at freshly polished and electrochemically pretreated electrodes

The contribution of the heterogeneous (involving non-adsorbed solution species) and surface path (involving adsorbed species) to the electrode processes of aromatic nitro compounds has been studied as a function of the surface conditions of glassy carbon (GC-20) by linear sweep voltammetry (LSV) and cyclic voltammetry (CV). The influence of adsorption was negligible at the freshly polished electrodes. Oxidative electrochemical pretreatment led to the formation of active sites at which the adsorption of the reactant resulted in enhanced electron-transfer rates. The nature of the adsorption process and the characteristics of the electrode reaction in the adsorbed state were studied in detail for p-nitrotoluene. The adsorption followed the Frumkin isotherm with an interaction parameter of 1.2, indicating moderate attractive interactions between the adsorbed molecules. The rate constant for the adsorbed species was of the order of 10⁵, higher than the apparent heterogeneous rate constant of p-nitrotoluene in the solution phase. The magnitude of the potential shift and the strength of adsorption varied with the relative position and electron-withdrawing power of the substituent in the aromatic ring of nitrobenzene. Free radical coupling was selectively catalysed at electrochemically pretreated electrodes.     

Intramolecular cyclization of nerol and the related (z)-allylic alcohols by means of TiCl4-PhNHMe complex. Synthesis of nezukone

Nerol is cyclized to terpinyl chloride or bromide in the presence of TiX₄-PhNHMe (1:1) complex in dichloromethane at ?23 °C, while cyclization of ($\text{Z}$)-allylic alcohols CH₂=CR-CH₂CH₂CMe=CHCH₂OH (R = H, Me, Cl) produces seven-membered ring products in fair yields.     

Aldol reaction of aluminium enolate resulting from 1,4-addition of Me2AlSPh to α,β-unsaturated carbonyl compound. A 1-acylethenyl anion equivalent

Me₂AlSPh or Me₂AlSeMe adds to α,β-unsaturated carbonyl compounds in 1,4-fashion. The resulting aluminium enolates react with aldehydes effectively to afford the adducts of the title anion after formal PhSH (or MeSeH)-elimination.     

A convenient and efficient method for incorporation of pentafluorosulfanyl (SF5) substituents into aliphatic compounds

Both SF₅Cl and SF₅Br undergo smooth, high yield addition to alkenes and alkynes under the mild free radical chain reaction conditions of triethylborane initiation at low temperature, although the SF₅Br chemistry is somewhat limited by its competing high electrophilic reactivity with electron rich alkenes. The SF₅Cl addition reaction is relatively insensitive to a wide variety of non-allylic functionalities.     

Preparation and properties of metallacyclobutanes of nickel and palladium

Bis(phosphine)-3,3-dimethylnickela- and palladacyclobutanes have been prepared by intramolecular C-H insertion reaction of the corresponding dineopentyl metal complexes. Nickelacyclobutane complexes decompose when heated thereby undergoing competitive carbon-carbon bond cleavage to give isobutene and ethylene, with reductive elimination affording 1,1-dimethylcyclopropane and skeletal isomeri-zation of the metallacyclic ring yielding 3-methyl-1-butene, whereas the palladium analog gave no significant amounts of CC bond cleavage products.Added phos-phine was seen to have an effect on CC bond scission of nickelacyclobutane complexes. Nickelacyclobutane complexes in solution are thought to be in equilibrium with olefin-coordinated nickel-carbene complex on the basis of available experimental evidence from hydrogenolysis, carbene-trap reactions with olefins and reaction with carbon monoxide     

XPS analysis of NH3 plasma-treated polystyrene films utilizing gas phase chemical modification

Gas phase chemical modification (GCM) is found to be more preferable as a pretreatment for the XPS surface analysis of polymer materials than the conventional liquid phase treatment because it can circumvent problems such as solvent contamination and swelling. We have tried the quantification of the surface composition successfully by estimating the yield of the reaction from model samples. GCM was then applied to correlate the surface composition of NH₃ plasma-treated polystyrene films with their cell-affinity. The amount of primary-amine and that of carboxylic acid were directly determined by GCM. Although the amount of primary-amine, 15–20% of total nitrogen, did not depend on the treatment intensity, the total amine content for the treated samples increased with the plasma treatment intensity. The quantity of carboxylic acid generated was found to be very small. All treated samples had better cell-affinity than the control. The sample N2 (of medium treatment) showed the best cell-affinity. The most strongly treated sample N3, with larger amine content than N2, showed worse cell-affinity because of the interference by the sputtered SiO₂ on the surface.