A supercooled imidazolium iodide ionic liquid as a low-viscosity electrolyte for dye-sensitized solar cells

A series of allyl-functionalized imidazolium salts are reported, including 1-allyl-3-ethylimidazolium iodide and 1-allyl-3-propylimidazolium iodide, which have melting points close to room temperature and show typical properties of supercooled fluids if heated above their melting points. Their viscosities in the liquid state are considerably lower than the benchmark ionic liquid used in solar cells, viz., 1-propyl-3-methylimidazolium iodide. Electrolytes containing these new liquids provide excellent efficiencies and good stability in dye-sensitized solar cells when subjected to an accelerated-light soaking test at 60 degrees C. The structures of three of the new salts have been established in the solid state by single-crystal X-ray analysis.     

High molar extinction coefficient heteroleptic ruthenium complexes for thin film dye-sensitized solar cells

Two novel heteroleptic sensitizers, Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-hexyloxystyryl)-2,2-bipyridine)(NCS)2 and Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-methoxystyryl)-2,2'-bipyridine) (NCS)2, coded as K-19 and K-73, respectively, have been synthesized and characterized by 1H NMR, FTIR, UV-vis absorption, and emission spectroscopy and excited-state lifetime and spectroelectrochemical measurements. The introduction of the alkoxystyryl group extends the conjugation of the bipyridine donor ligand increasing markedly their molar extinction coefficient and solar light harvesting capacity. The dynamics of photoinduced charge separation following electronic excitation of the K-19 dye was scrutinized by time-resolved laser spectroscopy. The electron transfer from K-19 to the conduction band of TiO2 is completed within 20 fs while charge recombination has a half-life time of 800 s. The high extinction coefficients of these sensitizers enable realization of a new generation of a thin film dye sensitized solar cell (DSC) yielding high conversion efficiency at full sunlight even with viscous electrolytes based on ionic liquids or nonvolatile solvents. An unprecedented yield of over 9% was obtained under standard reporting conditions (simulated global air mass 1.5 sunlight at 1000 W/m2 intensity) when the K-73 sensitizer was combined with a nonvolatile "robust" electrolyte. The K-19 dye gave a conversion yield of 7.1% when used in conjunction with the binary ionic liquid electrolyte. These devices exhibit excellent stability under light soaking at 60 degrees C. The effect of the mesoscopic TiO2 film thickness on photovoltaic performance has been analyzed by electrochemical impedance spectroscopy (EIS).     

一种新的求解带约束的有限极大极小问题的精确罚函数

提出了一种新的精确光滑罚函数求解带约束的极大极小问题．仅仅添加一个额外的变量,利用这个精确光滑罚函数,将带约束的极大极小问题转化为无约束优化问题． 证明了在合理的假设条件下,当罚参数充分大,罚问题的极小值点就是原问题的极小值点．进一步,研究了局部精确性质．数值结果表明这种罚函数算法是求解带约束有限极大极小问题的一种有效算法．     

Effect of nonlinear strain paths on forming limits under isotropic and anisotropic hardening

The path-dependence of the conventional Forming Limit Diagram (FLD) is an important issue for its applications in industry. Great efforts have been made to understand the nature of the path-dependence with both experimental and theoretical approaches, many of them attempting to find a path-independent way for the application of forming limits. In this paper, we focus on the nonlinear strain path effect on forming limit predictions using both isotropic and anisotropic hardening models. The Forming Limit Diagram (FLD), Forming Limit Stress Diagram (FLSD) and Forming Limit Effective Strain Diagram (epFLD) of sheet metals subject to linear and nonlinear strain paths are analyzed and compared using the Marciniak–Kuczynski approach. An anisotropic hardening model based on Yoshida and Uemori development is adopted in this study, and it is coupled with the traditional Hill’48 yield surface. This model is capable of describing the complex Bauschinger phenomenon after the material undergoes the reverse loading process such as the early re-yielding, work-hardening stagnation and permanent softening. Two different scenarios for the change of strain paths are also investigated. In the first scenario, the sheet material is initially loaded with a fixed strain increment ratio, unloaded to the free stress state, and then reloaded with a different strain increment ratio until the forming limit is reached. In the second scenario, the material does not undergo elastic unloading. Instead, the strain path is abruptly changed to a different strain increment ratio and the material undergoes continuous loading until the forming limit is reached. It is found that the work-hardening behavior after the pre-straining and the loading scenario plays an important role in the path dependent behavior of forming limits. Detailed analysis reveals that the M–K approach may have contributed to the significance of path-dependence observed in this study, especially at high pre-strain levels.     

Adsorption, capillary bridge formation, and cavitation in SBA-15 corrugated mesopores: a Derjaguin-Broekhoff-de Boer analysis

A Derjaguin-Broekhoff-de Boer analysis of adsorption and desorption in SBA-15 mesoporous silica is presented, using realistic geometrical models that account for the pore corrugation in these materials. The model parameters are derived from independent electron tomography and small-angle scattering characterization. A geometrical characteristic of the pore that is found to be important for adsorption is the corrugation length, l(C), which describes the longitudinal size of the geometrical defects along a given pore. Capillary bridges are possible only for large values of l(C). The results are explained in terms of two spinodal and two equilibrium pressures, characterizing the wide and the narrow sections of the pores. Simplified analytical expressions are obtained, which provide necessary conditions for bridge formation and for cavitation in terms of the radii of the narrow and wide sections of the pores, as well as of l(C). Quite generally, the results show that the deviation of the pore shape from that of ideal cylinders is key to understanding adsorption and desorption in corrugated mesopores, notably in SBA-15.     

Direct loading of polymer matrices in plastic microchips for rapid DNA analysis: A comparative study

We report the design and performance validation of microfluidic separation technologies for human identification using a disposable plastic device suitable for integration into an automated rapid DNA analysis system. A fabrication process for a 15-cm long hot-embossed plastic microfluidic devices with a smooth semielliptical cross section out of cyclic olefin copolymer is presented. We propose a mixed polymer solution of 95% w/v hydroxyethylcellulose and 5% w/v polyvinylpyrrolidone for a final polymer concentration of 2.5 or 3.0% to be used as coating and sieving matrix for DNA separation. This formulation allows preparing the microchip without pretreatment in a single-loading step and provides high-resolution separation (≈1.2 bp for fragments <200 bp), which is superior to existing commercial matrices under the same conditions. The hot-embossed device performance is characterized and compared to injection-molded devices made out of cyclic olefin copolymer based on their respective injector geometry, channel shape, and surface charges. Each device design is assessed by fluorescence videomicroscopy to evaluate the formation of injection plugs, then by comparing electropherograms for the separation of a DNA size standard relevant to human identification.     

Random Skew Plane Partitions with a Piecewise Periodic Back Wall

Random skew plane partitions of large size distributed according to an appropriately scaled Schur process develop limit shapes. In the present work, we consider the limit of large random skew plane partitions where the inner boundary approaches a piecewise linear curve with non-lattice slopes, describing the limit shape and the local fluctuations in various regions. This analysis is fairly similar to that in Okounkov and Reshetikhin (Commun Math Phys 269:571–609, 2007), but we do find some new behavior. For instance, the boundary of the limit shape is now a single smooth (not algebraic) curve, whereas the boundary in Okounkov and Reshetikhin (Commun Math Phys 269:571–609, 2007) is singular. We also observe the bead process introduced in Boutillier (Ann Probab 37(1):107–142, 2009) appearing in the asymptotics at the top of the limit shape.     

时间分辨全反射红外光谱对醋酸诱导丝蛋白构象转变的研究

采用时间分辨全反射红外光谱为主要分析手段, 对醋酸在丝蛋白膜中的扩散过程及其对丝蛋白构象转变机理进行了研究. 结果表明, 醋酸能够诱导丝蛋白构象转变为β-折叠. 醋酸的扩散速率和β-折叠构象的生成速率较为相似, 表明醋酸分子渗透到丝蛋白聚集体中是破坏丝蛋白原有氢键并诱导肽链重排, 进而实现构象转变的一个先决条件. 同时, 通过比较真空干燥处理前后丝蛋白膜的实验结果, 证实了丝蛋白中的水含量是影响醋酸的扩散速度以及丝蛋白多肽链重排速度的一个重要因素.