Computational studies on optoelectronic and charge transfer properties of some perylene‐based donor‐π‐acceptor systems for dye sensitized solar cell applications

We report DFT studies on some perylene‐based dyes for their electron transfer properties in solar cell applications. The study involves modeling of different donor‐π‐acceptor type sensitizers, with perylene as the donor, furan/pyrrole/thiophene as the π‐bridge and cyanoacrylic group as the acceptor. The effect of different π‐bridges and various substituents on the perylene donor was evaluated in terms of opto‐electronic and photovoltaic parameters such as HOMO‐LUMO energy gap, λ_max, light harvesting efficiency(LHE), electron injection efficiency (Ø_inject), excited state dye potential (E^dye*), reorganization energy(λ), and free energy of dye regeneration (). The effect of various substituents on the dye–I₂ interaction and hence recombination process was also evaluated. We found that the furan‐based dimethylamine derivative exhibits a better balance of the various optical and photovoltaic properties. Finally, we evaluated the overall opto‐electronic and transport parameters of the TiO₂‐dye assembly after anchoring the dyes on the model TiO₂ cluster assembly.     

染料敏化光催化还原水制氢

光敏化效应最早可追溯到大约170年前.早在1839年,Becquerel等人将氧化铜或卤化银涂在金属电极上,他们发现该电极在可见光照射下能够产生光电压[1].1887年,Vienna大学的Moser教授等人在卤化银电极上涂上染料赤藓红(erythrosine)的实验结果进一步证实了染料的光敏化效应[2].然而,直到德国科学家Tributsch等人在20世纪60年代阐释了染料吸附在半导体上并在一定条件下产生电流的机理,这一现象才引起广泛关注[3,4].     

Syntheses and Photophysical Properties of N‐Pyridylimidazol‐2‐ylidene Tetracyanoruthenates(II) and Photochromic Studies of Their Dithienylethene‐Containing Derivatives

A series of tetracyanoruthenate(II) with chelating pyridyl N‐heterocyclic carbene ligands (NHC‐py) was synthesized and characterized. Their photophysical and electrochemical properties as well as the photochromic behavior of their dithienylethene‐containing complexes were studied. Photocyclization was found to take place upon irradiation into the metal‐to‐ligand charge transfer (MLCT) absorption bands of these complexes, and evidence is provided to support the triplet‐sensitizing reaction pathway.     

Thermal loading induced near-infrared broadband upconversion emission of Sm-doped β-NaYbF4 nano-phosphors

A non-closed hydrothermal synthetic processing is improved to synthesize Sm³⁺ doped β-NaYbF₄ nano-phosphors at 98 °C without any high-temperature and high-pressure treatments as a final step. Novel green, red, and near-infrared broadband (799-873 nm) upconversion emissions of Sm³⁺-doped β-NaYbF₄ nano-phosphors under 980 nm excitation are observed. These UC emissions can be assigned to the Sm³⁺ transitions of ⁴G_J, ⁴F_3/2 and ⁶F_11/2→⁶H_J. The half-width of 873 nm emission band is broadened nearly two-fold through the annealing treatment for nano-phosphors. The upconversion process in Yb³⁺-Sm³⁺ system is discussed based on energy transfer mechanisms.     

Determination of Allosteric Effects and Interstrand Bidentate Interactions in DNA‐Peptide Molecular Recognition

To study DNA allostery, quantitative DNase I footprinting studies were carried out on a newly designed peptide His‐Hyp‐Lys‐Lys‐(Py)₄‐Lys‐Lys‐NH₂ (HypKK‐10) containing the XHypKK (Hyp = hydroxyproline) and polyamide motifs. The interconnection of DNA footprints of peptides HypKK‐10 and the parent peptide PyPro‐12 supports the proposal that interaction network cooperativity is preferred in DNA‐peptide interactions between multiple recognition sites. A simple method of determining interstrand bidentate interactions between the peptide moieties and DNA bases is introduced. It is envisaged that interstrand bidentate interactions also participate in the relay of conformational changes to recognition sites on the complementary strands. Circular dichroism studies of the titration of peptide HypKK‐10 with an oligonucleotide duplex indicate that this peptide binds in a dimeric fashion to DNA in the minor groove. This work may prompt the design of new DNA binding ligands for the study of DNA‐peptide allosteric interactions and DNA interaction network.     

广告分担、价格折扣与供应链的纵向合作广告

研究了生产商和零售商的纵向合作广告问题。分别在广告分担和价格折扣策略下，探讨了双方的均衡结果和利润。当生产商的边际利润较小时，生产商的最优决策是不采取任何一种策略。当生产商的边际利润达到一定范围时，广告分担策略是双方共同的最优选择。而无论在什么样的条件内，价格折扣策略都不会使双方同时满意。为了增加双方的收益，供应链成员应该在广告上集成决策。最后给出了系统集成的可行最优解的范围和Nash讨价还价解。