Reversibly Switchable Fluorescent Molecular Systems Based on Metallacarborane–Perylenediimide Conjugates

Icosahedral metallacarboranes are θ-shaped anionic molecules in which two icosahedra share one vertex that is a metal center. The most remarkable of these compounds is the anionic cobalt-based metallacarborane [Co(C₂B₉H₁₁)₂]⁻, whose oxidation-reduction processes occur via an outer sphere electron process. This, along with its low density negative charge, makes [Co(C₂B₉H₁₁)₂]⁻ very appealing to participate in electron-transfer processes. In this work, [Co(C₂B₉H₁₁)₂]⁻ is tethered to a perylenediimide dye to produce the first examples of switchable luminescent molecules and materials based on metallacarboranes. In particular, the electronic communication of [Co(C₂B₉H₁₁)₂]⁻ with the appended chromophore unit in these compounds can be regulated upon application of redox stimuli, which allows the reversible modulation of the emitted fluorescence. As such, they behave as electrochemically-controlled fluorescent molecular switches in solution, which surpass the performance of previous systems based on conjugates of perylendiimides with ferrocene. Remarkably, they can form gels by treatment with appropriate mixtures of organic solvents, which result from the self-assembly of the cobaltabisdicarbollide-perylendiimide conjugates into 1D nanostructures. The interplay between dye π-stacking and metallacarborane electronic and steric interactions ultimately governs the supramolecular arrangement in these materials, which for one of the compounds prepared allows preserving the luminescent behavior in the gel state.     

氮气介质高气压开关特性

从理论分析、软件模拟、实验研究等方面研究了氮气介质高气压开关的工作特性。根据强度理论计算所设计并加工的开关的理论压强可达10 MPa。对氮气介质高气压开关进行实验,得到在气压范围2,4,6 MPa、电极间隙0.1,0.5,1.0 mm时,气隙的击穿延时小于14 ns,抖动小于1 ns;在气压2 MPa、电极间隙0.1 mm时50%击穿电压约为34 kV。与常压空气开关相比较,该开关具有很好的稳定性和绝缘特性。     

光学薄膜中节瘤缺陷研究进展

结合本实验室及国内外同行的工作进展,概括性地介绍了光学薄膜中节瘤缺陷的生长特性、结构特征和损伤特性,以及激光预处理和破坏修复技术的研究进展。节瘤种子的尺寸、形状和表面特性决定了节瘤缺陷的尺寸、边界结构的连续性和表面形貌特征。节瘤种子的来源主要有基底加工和清洗过程的残留物,镀膜过程中真空室的污染和蒸发材料的喷溅,并给出了相应的抑制方法。节瘤的电场增强效应是导致节瘤缺陷易损伤的另一个重要原因。节瘤缺陷的激光预处理和破坏坑的修复技术可以提高光学薄膜的抗激光损伤能力。     

Radiation chemistry of tris(acetylacetonato) cobalt(iii) in aqueous solutions

Abstract

On radiolysis tris(acetylacetonato) cobalt(III) in aqueous solutions is found to get reduced by reaction with (1) hydrated electrons, (2) H atoms, (3) OH radicals and (4) C₂H₂OH radicals. The bimolecular rate constants for the first three reactions, determined by competition kinetics are: 4 × 10¹⁰, 2.3 × 10⁹ and 4.7 × 10⁹ M^?1sec^?1 respectively. Absorption spectra of the irradiated solutions indicate the formation of bis(acetylacetonato) cobalt(II) from reaction (1), but not from (3). The total cobaltous yield in air-free solutions is given byG(Co⁺⁺) = 5.6 and 6.5 at pH 6.5 and 1 respectively. It appears that G_eaq- ∽ _H ⁺ G_oH ∽ 2.8 in neutral solutions. Considerations of material balance for the primary yields of radiolysis of water suggest the possibility that the so-called independent H-atoms in neutral solutions are probably excited water molecules or ion-pairs.     

Defect-effects on the photoluminescence of ZrO2 bulk,film and nanocrystals

The photoluminescence (PL) properties of ZrO₂ have been measured at different temperatures between 7 and 300 K, using various kinds of ZrO₂ specimens: bulk crystal melt-grown by a large solar furnace, thermally oxidized zirconium plate (ZrO₂ film crystal on Zr ) and nanocrystals (surface area: 35–45m²/g, diameter: 20–30 nm). The results clarify the deep and shallow energy level structures in the energy gap. Reversible UV-laser-light-induced spectral changes are observed for all of the specimens in different specimen-atmospheres (vacuum and O₂ gas). The results elucidate the defect-effects of the PL properties and the PL enhancement mechanism in ZrO₂ nanocrystals.     

In vitro metabolism study of Strychnos alkaloids using high‐performance liquid chromatography combined with hybrid ion trap/time‐of‐flight mass spectrometry

In this report, the in vitro metabolism of Strychnos alkaloids was investigated using liquid chromatography/high‐resolution mass spectrometry for the first time. Strychnine and brucine were selected as model compounds to determine the universal biotransformations of the Strychnos alkaloids in rat liver microsomes. The incubation mixtures were separated by a bidentate‐C₁₈ column, and then analyzed by on‐line ion trap/time‐of‐flight mass spectrometry. With the assistance of mass defect filtering technique, full‐scan accurate mass datasets were processed for the discovery of the related metabolites. The structural elucidations of these metabolites were achieved by comparing the changes in accurate molecular masses, calculating chemical component using Formula Predictor software and defining sites of biotransformation based upon accurate MSⁿ spectral information. As a result, 31 metabolites were identified, of which 26 metabolites were reported for the first time. These biotransformations included hydroxylation, N‐oxidation, epoxidation, methylation, dehydrogenation, de‐methoxylation, O‐demethylation, as well as hydrolysis reactions. Copyright © 2013 John Wiley & Sons, Ltd.     

Gastrennung mit Hilfe des Zirkulations-Diffusions-Verfahrens Teil I : Hochanreicherung von Gasen in Trennrohren mit natürlicher Zirkulation

Auf der Grundlage des Zirkulations-Diffusions-Prinzips wurden zwei Trennrohre für die Hochanreicherung von Gasen enytwickelt. Als Modellgasmischungen dienten H₂-N₂ Kr-CH₄ und Luft. Neben Wasserdampf wurden Methanol- und Äthaanoldämpfe als Treibmittel benutzt. Gute Trennungen wurden in einem nur 20 cm langen Rohr erzielt, dessen Trennspalt horizontal durch Lamellen in kleine Sektionen und durch ein Drahtdiaphragma vertikal in zwei Ringkammern geteilt wird. Drei Rohre dieses Typs wurden in einer rechteckigen Kaskadenanordnung getestet. Die Theorie des Transportes im Trennrohr sowie die Behandlung des hydrodynamischen Problems werden angegeben. Eine Anwendung des beschriebenen Trennrohres zur Isotopentrennung und zur Gashochanreicherung erscheint aussichtsreich.     

Studies on defect formation in femtosecond laser-irradiated PMMA and PDMS

We report here our results on the spectroscopic and elemental analysis of femtosecond (fs) laser-modified regions in polymers of polymethylmethacrylate (PMMA) and polydimethylsiloxane (PDMS) in the context of defect formation and emission in the visible region. Different physical and chemical models are used to explain the changes in modified regions. We found that the emission intensity, recorded from the fs-modified regions of polymers, decreased over time to a constant value. We also demonstrate that these materials are suitable for the preparation of the microstructures en route for light guiding applications. The fs laser-irradiated regions exhibited paramagnetic behavior as was confirmed from electron spin resonance studies through the formation of peroxide-type free radicals. Raman mapping was performed in the modified regions which consisted of defects and found that the modulations in intensity are predominant in the central portion of the structure compared to edges. Elemental analysis has been performed in the modified regions using field emission scanning electron microscope instrument and energy-dispersive X-ray absorption spectroscopy to estimate the percentage contents of individual elements which resulted in defect formation such as paramagnetic and optical centers.