Conjugation of Selenophene with Bipyridine for a High Molar Extinction Coefficient Sensitizer in Dye-Sensitized Solar Cells

A high molar extinction coefficient heteroleptic polypyridyl ruthenium sensitizer, featuring a conjugated electron-rich selenophene unit in its ancillary ligand, has been synthesized and demonstrated as an efficient sensitizer in dye-sensitized solar cells. A nanocrystalline titania film stained with this sensitizer shows improved optical absorptivity, which is highly desirable for dye-sensitized solar cells with a thin photoactive layer. With preliminary testing, this sensitizer has already achieved a high efficiency of 10.6% measured under the air mass 1.5 global conditions.

An Extremely High Molar Extinction Coefficient Ruthenium Sensitizer in Dye-Sensitized Solar Cells: The Effects of pi-Conjugation Extension

We report a heteroleptic ruthenium complex (007) featuring the electron-rich 5-octyl-2,2'-bis(3,4-ethylenedioxythiophene) moiety conjugated with 2,2-bipyridine and exhibiting 10.7% power conversion efficiency measured at the AM1.5G conditions, thanks to the enhanced light-harvesting that is closely related to photocurrent. This C107 sensitizer has an extremely high molar extinction coefficient,of 27.4 x 10(3) M-1 cm(-1) at 559 nm in comparison to its analogue C103 (20.5 x 10(3) M-1 cm(-1) at 550 nm) or Z907 (12.2 x 10(3) M(-1)cm(-1) at 521 nm) with the corresponding 5-hexyl-3,4-ethylenedioxythiopliene- or nonyl-substituted bipyridyl unit. The augmentation of molar extinction coefficients and the bathochromic shift of low-energy absorption peaks along with the pi-conjugation extension are detailed by TD-DFT calculations. The absorptivity of mesoporous titania films grafted with Z907, C103, or C107 sublinearly increases with the molar extinction coefficient of sensitizers, which is consistent with the finding derived from the surface coverage measurements that the packing density of those sensitizers decreases with the geometric enlargement of ancillary ligands.

Prediction of molar absorptivities of color reagents and their color reactions with yttrium by artificial neural networks

The new topological indices A(x1)-A(x3) suggested in our laboratories were applied to the study of structure-property relationships between color reagents and their color reactions with yttrium. The topological indices of twenty asymmetrical phosphone bisazo derivatives of chromotropic acid were calculated. The work shows that QSPR can be used as a novel aid to predict the molar absorptivities of color reactions and in the long term to be helpful tool in-color reagent design. Multiple regression analysis and neural network were employed simultaneously in this study. The results demonstrated the feasibility and the effectiveness of the method.

Studies on the nature of the macromolecular condensed state of "nascent" ultra high molar mass polyethylene

Ultra high molar mass polyethylene (UHPE) powder as polymerized in a slurry process has been studied, in its nascent state, after recrystallization on rapid cooling from the melt and after hot compression molding to a film, by DSC, effect of annealing the recrystallized specimen at 120 similar to 130 degreesC, morphology by polarizing optical microscopy and small angle X-ray scattering. Based on the experimental results obtained the macromolecular condensed state of the nascent UHPE powder is a rare case of a multi-chain condensed state of non-interpenetrating chains, involving interlaced extended chain crystalline layers and relaxed parallel chain amorphous layers. On melting, a nematic rubbery state of nanometer size domain resulted. The nematic-isotropic transition temperature was judged from literature data to be at least 220 degreesC, possibly higher than 300 degreesC, the exact temperature is however not sue because of chain degradation at such high temperatures. The recrystallization process from the melt is a crystallization from a nematic rubbery state. The drop of remelting peak temperature by 10 K of the specimen recrystallized from its melt as compared to the nascent state has its origin in the decrease both of the crystalline chain stem length and of the degree of crystallinity. The remelting peak temperature could be returned close to that of the nascent state by annealing at 120 similar to 130 degreesC.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 6. Structure changes from smectic to columnar phases in a series of copolyethers containing odd and even numbers of methylene units in equal molar composition

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

Laser light scattering studies of soluble high-performance polyimides: Solution properties and molar mass distributions

Two soluble high-performance polyimides, poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA), in CHCl3 at 25 degrees C have been studied using laser light scattering. We found that the z-average radius of gyration ([R(g)]) can be scaled to the weight-average molecular weight (M(w)) as [R(g)] (nm) = 4.95 x 10(-2)M(w)(0.52) and [R(g)] (nm) = 1.25 x 10(-2)M(w)(0.66) respectively for poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA), indicating that poly(ODPA/DMMDA) in CHCl3 at 25 degrees C has a more extended chain conformation than poly(BCPOBDA/DMMDA). Using the wormlike chain model approach, we found that the Flory characteristic ratios (C*) of poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA) are similar to 20 and similar to 31, respectively, indicating that both of them have a slightly extended chain conformation in comparison with typical flexible polymer chains, such as polystyrene, whose C-infinity is similar to 10. A combination of the weight-average molar mass (M(w)) with the translational diffusion coefficient distributions (G(D)) has led to D (cm(2)/s) = 3.53 x 10(-4)M(-0.579) and D (cm(2)/s) = 4.30 x 10(-4)M(-0.613) respectively for two soluble high-performance polyimides, poly(BCPOBDA/DMMDA) and poly(ODPA/DMMTA), in CHCl3 at 25 degrees C. Using these two calibrations, we have successfully characterized the molar mass distributions of the two polyimides from their corresponding G(D)s. The exponents of these two calibrations further confirm that both of the polyimides have a slightly extended coil chain conformation in CHCl3. The chain flexibility difference between these two polyimides has also been discussed.

Prediction of molar absorptivities of color reagents during their color reactions with cerium using multiple regression analysis and neural network

A quantitative structure-property study has been made on the relationship between molar absorptivities (epsilon) of asymmetrical phosphone bisazo derivatives of chromotropic acid and their color reactions with cerium by multiple regression analysis and neural network. The new topological indices A(x1) - A(x3) suggested in our laboratory and molecular connectivity indices of 43 compounds have been calculated. The results obtained from the two methods are compared. The neural network model is superior to the regression analysis technique and gave a prediction which was sufficiently accurate to estimate the molar absorptivities of color reagents during their color reactions with cerium.

Spectral changes of C-phycocyanin with different molar ratios of SPDP

Pure C-phycocyanin was prepared from Spirulina platensis using one-step anion-exchange chromatography. The C-PC obtained was with an absorption maximum at 620 nm and a fluorescence emission maximum at 640 nm when excited by 580 nm. SPDP is an excellent heterobifunctional crosslinker for thiolating amines. Different molar ratios of SPDP have remarkable influence on the absorption and fluorescence spectra of C-phycocyanin. The absorption maximum and fluorescence emission maximum both decreased and blue-shifted from 640 run to 630 nm as the molar ratios of SPDP increased. It was found that the molar ratios of SPDP to C-phycocyanin was not more than 100 was appropriate to being conjugated with other biomolecules from the absorption and fluorescence spectra of C-phycocyanin.

Enhancement of molar heat capacity of nanostructured Al2O3

The nanosized alumina prepared by the hydrolysis method with an average particle size of 20 nm was characterized by X-ray diffraction. The heat capacity measurements of the prepared sample were carried out using an adiabatic calorimeter in the temperature range from 78 to 370 K. Enhancement of heat capacity was observed in the nanostructured materials as the heat capacity data were compared with those of the corresponding coarse-grained materials. The enhanced heat capacity was discussed on the basis of experiments. Differential scanning calorimetry and thermogravimetry were used to determine the thermal stability of the nanostructured alumina.

Avaliação do sistema radicular e de rizomas de um campo natural diferido em Bagé, RS.

A utilização do Campo Sulino natural na pecuária de forma cada vez mais intensa e constante tem provocado a diminuição da sua condição produtiva. A excessiva remoção da parte aérea afeta o desenvolvimento das raízes. Um sistema radicular bem desenvolvido permite às plantas forrageiras explorar maior volume de solo, melhorando a absorção de água e nutrientes. As raízes também funcionam como órgão de reserva, assegurando rápida rebrota e produtividade das plantas forrageiras. O diferimento é uma prática de manejo de pastagens que pode ajudar a recuperar o campo por meio de descanso programado durante um tempo determinado. Este trabalho avaliou o efeito do tratamento de diferimento sobre o sistema radicular de campo natural após três anos de aplicação (agosto de 2000 a julho de 2003) na Embrapa Pecuária Sul (Bagé, RS). As avaliações foram realizadas no campo com presença animal durante todo o ano e sob diferimento de verão/outono (sem animais na área de março a junho). Foram coletadas 18 amostras de solo em cada tratamento, nas profundidades de 0?10 cm e 10?20 cm. As raízes e os rizomas foram separados do solo e entre si, secos e pesados. Houve diferença (p<0,05) para a porcentagem de raízes e a massa da matéria seca de rizomas. A testemunha apresentou 83,98% das raízes na camada de 0?10 cm e o diferimento, 77,5%. Na camada de 10?20 cm, sob diferimento houve aumento de 35% de raízes em relação à testemunha. A maior massa de matéria seca de rizomas foi obtida em pastagem sob diferimento, com 106% a mais em comparação à testemunha. Os resultados indicam vantagem do descanso da pastagem dos Campos Sulinos, tanto no acúmulo de reservas (maior quantidade de rizomas) voltado à propagação de gramíneas rizomatosas de interesse, quanto também no desenvolvimento de raízes na camada de 10?20 cm.

Ciclos de seleção e modificações na anatomia radicular do milho Saracura sob alagamento.

O alagamento é um problema encontrado em diversas áreas com potencial agrícola, afetando principalmente os produtores mais pobres. O milho ?Saracura? BRS 4154 foi desenvolvido no intuito de possibilitar o seu plantio em regiões sujeitas ao alagamento, estando atualmente no seu 18° ciclo de seleção. O presente trabalho teve como objetivos verificar as modificações nas características anatômicas radiculares relacionadas com o alagamento e o seu incremento ou não ao longo dos 18 ciclos de seleção em comparação com 2 variedades controle (BR 107 e BRS 1010) submetidas ao alagamento intermitente de 2 dias. As amostras radiculares foram preparadas pelas microtécnicas apropriadas e analisadas em microscopia óptica. Foram observados em relação ao grupo controle e aos ciclos anteriores: aumentos na capacidade de formação de aerênquima; diminuição no córtex; diminuição no diâmetro dos vasos; diminuição da camada subepidérmica; aumento na espessura do floema; e epiderme. Dessa forma, os sucessivos ciclos de seleção foram capazes de melhorar as características do milho Saracura e a sua adaptabilidade a ambientes alagados.

Anatomia radicular ao longo dos ciclos de seleção do milho Saracura sob alagamento intermitente do solo.

Este trabalho foi realizado com o objetivo de caracterizar as modificações nas estruturas anatômicas radiculares em sucessivos ciclos de seleção (ciclo 1 ao ciclo 18 alternados) do milho Saracura BRS 4154 sob encharcamento do solo. Essa variedade possui capacidade de sobreviver e produzir em solos temporariamente alagados e foi desenvolvida, pela Embrapa Milho e Sorgo, por seleção recorrente fenotípica estratificada para plantio em solos de várzea. O ensaio foi conduzido em condições de campo, iniciando o alagamento do solo no estádio de seis folhas, aplicando uma lâmina de 20 cm de água três vezes por semana. No florescimento, amostras de raízes foram retiradas, fixadas e seccionadas para observação em microscópio de luz. Pelas fotomicrografias de secções transversais, foi observada, ao longo dos ciclos de seleção, maior quantidade de aerênquima, diminuição do córtex, diminuição da exoderme, aumento na proporção do cilindro vascular, metaxilemas menores e numerosos e aumento na espessura do floema e da epiderme. Essas modificações proporcionaram à planta de milho maior adaptação, aumentando sua capacidade de tolerar solos encharcados.

Metodologia de análise do sistema radicular, em solo, de genótipos de sorgo selecionados previamente para eficiência no uso de fósforo.

2010

Podridão radicular de fitóftora em soja.

2007