Investigation of aromaticity and photophysical properties in [18]/[20]π porphycene derivatives

In this study, we have investigated the relationship between aromaticity and photophysical properties of trifluoromethyl-substituted [18]/[20]π porphycenes by using theoretical calculations and various spectroscopic methodologies. Interestingly, we have found that the HOMO-LUMO gap of [20]π porphycene is larger than that of [18]π porphycene, which is in a sharp contrast with those of typical [4n]/[4n+2]π porphyrinoids. Based on our observations, we demonstrate that the origin of this contrasting feature of [20]π porphycene arises from the uniquely large energy splitting between LUMO and LUMO+1 of [18]π porphycene compared with other aromatic [4n+2]π porphyrinoids with nearly degenerate LUMO/LUMO+1. Consequently, we can propose that the energy difference between LUMO and LUMO+1 levels of aromatic [4n+2]π porphyrinoids is an important factor in determining the electronic nature of their corresponding antiaromatic [4n]π porphyrinoids. Moreover, to the best of our knowledge, this is the first study to illustrate the photophysical properties of porphycenes with [4n]π electronic circuits.     

Synthesis and properties of delafossite CuAlO<Subscript>2</Subscript> nanowires

Ultra-long and uniform CuAlO₂ nanowires were successfully synthesized within a porous anodic aluminum oxide template by means of sol–gel method at 900 °C. The results of X-Ray diffraction indicate that the obtained CuAlO₂ nanowires have a single delafossite structure. The scanning electron microscopy and transmission electron microscopy show that the CuAlO₂ nanowires have a uniform diameter with about 50 nm and a length up to 10 μm. Room-temperature photoluminescence measurement of nanowires exhibits an ultraviolet near-band-edge emission around 350 nm (3.54 eV).     

Porous Pr(OH)(3) Nanostructures as High-Efficiency Adsorbents for Dye Removal

Herein we report the electrochemical synthesis of porous Pr(OH)(3) nanobelt arrays (NBAs), nanowire arrays (NWAs), nanowire bundles (NWBs), and nanowires (NWs) and their applications as dye absorbents in water treatment. These Pr(OH)(3) nanostructures exhibit high efficient and selective adsorption of the dyes with amine (-NH(2)) functional groups such as Congo red, reactive yellow, and reactive blue. The high efficiency and selectivity is attributed to the large effective surface area of the porous structure, plentiful hydroxyl groups, and basic sites on the Pr(OH)(3) surface. Furthermore, the toxicity studies of these porous Pr(OH)(3) nanostructure show a negligible effect on seed germination, indicating that they hold great potential as environmentally friendly absorbents in water treatment.     

脂肪酸多聚甘油酯分子结构与性能相关性研究

采用量子化学MM+和AM1方法计算聚甘油和脂肪酸多聚甘油酯的分子结构参数,然后用逐步线性回归方法建立脂肪酸多聚甘油酯HLB值的定量结构性质(QSPR)模型,所得的预测模型中包含四个参数(单位质量分子所含氧原子数Xo、生成热ΔfHm、电子能Ee和水合能Eh),预测值及外部检验的复相关系数(R2)和标准偏差(SD)分别为0.9553、0.73722和0.9678、6.34426。结果表明,量子化学方法计算简单,对脂肪酸多聚甘油酯结构的表征能力较强,所建QSPR模型具有能较好的预测能力和较强的稳健性,并在一定程度上阐明了脂肪酸多聚甘油酯分子结构与性能之间的关系。     

Ionic liquid self‐assembled monolayer and ion exchange for surface force control

Adhesion and lateral force were controlled by the formation of a self‐assembled monolayer combined with the surface ion exchange of ionic liquids on a silicon surface. In this study, the functionalized imidazolium ionic liquids were designed and synthesized with the aim of controlling surface force. N‐[3‐(Trimethoxylsilyl)propyl] ethylenediamine molecules were first self‐assembled onto a surface as an anchor layer and then 1‐propionic acid‐3‐methylimidazolium chloride were successfully grafted onto the amino‐modified surface. The surface force was changed by surface ion exchange in various anionic solutions. The self‐assembly and ion exchange processes were detected by means of attenuated total reflectance‐Fourier transform infrared spectrometry and further confirmed by X‐ray photoelectron spectra. Adhesion and friction behaviors were systematically investigated by atomic force/friction force microscope. The results indicated that anions played a great role in determining surface properties. Furthermore, surface adhesion and friction can be possibly quantitatively determined by the counter‐anions on the surface. Copyright © 2011 John Wiley & Sons, Ltd.     

A simple, high sensitivity mutation screening using Ampligase mediated T7 endonuclease I and Surveyor nuclease with microfluidic capillary electrophoresis

Mutation and polymorphism detection is of increasing importance for a variety of medical applications, including identification of cancer biomarkers and genotyping for inherited genetic disorders. Among various mutation-screening technologies, enzyme mismatch cleavage (EMC) represents a great potential as an ideal scanning method for its simplicity and high efficiency, where the heteroduplex DNAs are recognized and cleaved into DNA fragments by mismatch-recognizing nucleases. Thereby, the enzymatic cleavage activities of the resolving nucleases play a critical role for the EMC sensitivity. In this study, we utilized the unique features of microfluidic capillary electrophoresis and de novo gene synthesis to explore the enzymatic properties of T7 endonuclease I and Surveyor nuclease for EMC. Homoduplex and HE DNAs with specific mismatches at desired positions were synthesized using PCR (polymerase chain reaction) gene synthesis. The effects of nonspecific cleavage, preference of mismatches, exonuclease activity, incubation time, and DNA loading capability were systematically examined. In addition, the utilization of a thermostable DNA ligase for real-time ligase mediation was investigated. Analysis of the experimental results has led to new insights into the enzymatic cleavage activities of T7 endonuclease I and Surveyor nuclease, and aided in optimizing EMC conditions, which enhance the sensitivity and efficiency in screening of unknown DNA variations.     

Metal-free synthesis of allylic amines by cross-dehydrogenative-coupling of 1,3-diarylpropenes with anilines and amides under mild conditions

Dehydrogenative cross-coupling reaction of primary anilines, secondary anilines, carboxamides, and sulfonamides with 1,3-diarylpropenes to form a series of allylic amines promoted by DDQ have been realized. Both monoallylation and diallylation products can be selectively synthesized when primary anilines are used as the starting materials. The method may provide a wide scope of allylamines in scientific research including biologically active compound library construction.     

Structure flexibility of the Cu2ZnSnS4 absorber in low-cost photovoltaic cells: from the stoichiometric to the copper-poor compounds

Here we present for the very first time a single-crystal investigation of the Cu-poor Zn-rich derivative of Cu(2)ZnSnS(4). Nowadays, this composition is considered as the one that delivers the best photovoltaic performances in the specific domain of Cu(2)ZnSnS(4)-based thin-film solar cells. The existence of this nonstoichiometric phase is definitely demonstrated here in an explicit and unequivocal manner on the basis of powder and single-crystal X-ray diffraction analyses coupled with electron microprobe analyses. Crystals are tetragonal, space group I ?4, Z = 2, with a = 5.43440(15) ? and c = 10.8382(6) ? for Cu(2)ZnSnS(4) and a = 5.43006(5) ? and c = 10.8222(2) ? for Cu(1.71)Zn(1.18)Sn(0.99)S(4).     

The Effect of Cross‐Linking on the Actuation of an Electroactive IPMC Prepared with a Fluorinated Acrylic Copolymer

The hydroxyl group of HEMA was cross‐linked with 1,3‐diethoxy‐1,1,3,3‐tetramethyldisiloxane in order to enhance the actuation force of the ionic polymer‐metal composite (IPMC) made from the acrylic ter‐polymer of fluoroalkyl methacrylate, 2‐acylamido‐2‐methyl‐1‐propanesulfonic acid, and 2‐hydroxyethyl methacrylate (HEMA). The water uptake was reduced and the mechanical strengths of the membrane were improved by the cross‐linkage. The actuation force of the IPMC was generally enhanced, although it was reduced somewhat at high levels of cross‐linking. The current and deformation responses of the IPMC were both decreased by cross‐linking.     

High Optical Transparency and Low Dielectric Constant Polyimides Containing Trifluoromethyl and Cyclohexane Groups

A series of novel polyimides (PIs) were polymerized from 4,4′-(cyclohexane-1,4-diylbis (oxy))bis(3-(trifluoromethyl)aniline) (1) and 1,4-bis((4-amino-2-(trifluoromethyl) phenoxy)methyl)cyclohexane (2), with two aromatic tetracarboxylic dianhydrides using the typical one-step method. The inherent viscosity of these resulting PIs were in the range of 0.53–0.91 dl/g in N,N-dimethylacetamide (DMAc) at 30°C. They were readily soluble in numerous solvents, such as N-methyl-2-pyrrolidone (NMP), DMAc, N,N-dimethylformamide (DMF), meta-cresol (m-Cresol), and dimethylsulfoxide (DMSO). The PI films showed high optical transparency and were colorless with an ultraviolet-visible absorption cut-off wavelength around 330 nm, and a low dielectric constants of 2.49–2.93 at 1 MHz. The PIs also showed good thermal properties. Their glass-transition temperatures (T _g) were higher than 337°C, and the temperatures of 10% weight loss in air and nitrogen were higher than 412°C and 417°C. Furthermore, the PI films possessed good mechanical properties with tensile strengths of 54–71 MPa, elongations at break of 11.6%–17.3% and low moisture absorption (<1.34%). Due to their properties, these PIs could be considered as materials for photoelectric and micro-electronic applications.