Novel carboxylated pyrrole- and carbazole-based monomers. Synthesis and electro-oxidation features

Carboxylated pyrrole (Pyr, a index)- and carbazole (Cbz, b index)-containing monomers 6-7a/b and 9a/b have been readily synthesized from the monobenzyl ester of L-glutamic acid and triamine 2 using Clauson-Kaas and amide coupling reactions. In contrast to Pyr-containing compounds 6-7a, and 9a, the three Cbz-containing monomers 6-7b, and 9b have been found electroactive and were successfully electropolymerized on a Pt electrode resulting in the deposition of corresponding insoluble electroconducting polyCOOH polyCbz-films poly(6-7b) and poly(9b).     

Impact of interstitial air holes on a wide-bandwidth rejection filter made from a photonic crystal fiber

We have investigated the spectral properties of a band rejection filter made with a long-period fiber grating written in photonic crystal fiber that has interstitial air holes. Experiments showed that only one mode was coupled strongly to the fundamental core mode over a 600 nm spectral range. The central wavelength of the filter could be tuned over that range without being appreciably affected by any other mode. By using the multipole method, we found that the interstitial air holes of the photonic crystal fiber played a critical role in limiting the number of modes that could strongly interact with the fundamental mode and in obtaining well-separated resonance peaks. Excellent agreement between theory and experiment was obtained.     

High-spectral-resolution coherent anti-Stokes Raman scattering with interferometrically detected broadband chirped pulses

To achieve high-spectral-resolution multiplex coherent anti-Stokes Raman scattering (CARS), one typically uses a narrowband pump pulse and a broadband Stokes pulse. This is to ensure a correspondence between anti-Stokes and vibrational frequencies. We obtain high-resolution CARS spectra of isopropanol, using a broadband chirped pump pulse and a broadband Stokes pulse, by detecting the anti-Stokes pulse with spectral interferometry. With the temporally resolved anti-Stokes signal, we can remove the chirp of the anti-Stokes pulse and restore high spectral resolution while also rejecting nonresonant scattering.     

氩氧流量比对CeOx-SnOx膜微观结构及光学性能的影响

采用磁控反应共溅射的方法,以金属Ce和Sn为金属源,成功地制备出CeOx-SnOx薄膜.利用扫描电子显微镜(SEM)、X射线衍射(XRD)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等测试手段对薄膜的结构、表面形貌及成分进行了分析和表征.结果表明薄膜以岛状模式生长,随氩氧比降低,结晶性增强,出现CeO2和SnO相.此外,利用紫外-可见分光光度计对薄膜的光学性能进行了研究,测试结果表明薄膜对紫外光有极强的吸收作用.当氩氧流量比为3∶1时,紫外光平均透过率仅为5.80;,而可见光平均透过率为81.48;.     

Effect of Sulfonation Degree on Performance of Proton Exchange Membranes for Direct Methanol Fuel Cells

A series of proton exchange membranes based on sulfonated polyarylene ether ketones(SPAEKs) was used to study the effect of sulfonation degree on proton conductivity, methanol permeation and performance of direct methanol fuel cells(DMFCs). Dependences of physical characteristics of the membranes, i. e., proton conductivity, water uptake, swelling ratio, methanol permeability and ion exchange capacity(IEC) were systematically studied. Both methanol permeability and proton conductivity of the SPAEK membrane grow rapidly as the increase in sulfonation degree since methanol molecules and protons share the same transfer channel. However,the methanol permeability plays more important role comparing to proton conductivity. As a result, the SPAEK membrane with a medium sulfonation degree(60%) was found to yield the best performance in a DMFC due to the acquirement of balanced conductivity and methanol permeability.     

Competition between singlet fission and charge separation in solution-processed blend films of 6,13-bis(triisopropylsilylethynyl)pentacene with sterically-encumbered perylene-3,4:9,10-bis(dicarboximide)s

The photophysics and morphology of thin films of N,N-bis(2,6-diisopropylphenyl)perylene-3,4:9,10-bis(dicarboximide) (1) and the 1,7-diphenyl (2) and 1,7-bis(3,5-di-tert-butylphenyl) (3) derivatives blended with 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn) were studied for their potential use as photoactive layers in organic photovoltaic (OPV) devices. Increasing the steric bulk of the 1,7-substituents of the perylene-3,4:9,10-bis(dicarboximide) (PDI) impedes aggregation in the solid state. Film characterization data using both atomic force microscopy and X-ray diffraction showed that decreasing the PDI aggregation by increasing the steric bulk in the order 1 < 2 < 3 correlates with a decrease in the density/size of crystalline TIPS-Pn domains. Transient absorption spectroscopy was performed on ~100 nm solution-processed TIPS-Pn:PDI blend films to characterize the charge separation dynamics. These results showed that selective excitation of the TIPS-Pn results in competition between ultrafast singlet fission ((1*)TIPS-Pn + TIPS-Pn → 2 (3*)TIPS-Pn) and charge transfer from (1*)TIPS-Pn to PDIs 1-3. As the blend films become more homogeneous across the series TIPS-Pn:PDI 1 → 2 → 3, charge separation becomes competitive with singlet fission. Ultrafast charge separation forms the geminate radical ion pair state (1)(TIPS-Pn(+?)-PDI(-?)) that undergoes radical pair intersystem crossing to form (3)(TIPS-Pn(+?)-PDI(-?)), which then undergoes charge recombination to yield either (3*)PDI or (3*)TIPS-Pn. Energy transfer from (3*)PDI to TIPS-Pn also yields (3*)TIPS-Pn. These results show that multiple pathways produce the (3*)TIPS-Pn state, so that OPV design strategies based on this system must utilize this triplet state for charge separation.     

Computer experiment and global optimization of layered monocentric lens systems

In this paper we derive a general analytical solution for a monocentric lens system and present a global optimization method combining sequential design for global optimization and an expected improvement algorithm for global optimization for the design and analysis of a layered monocentric lens system, which provides an “intelligent” way to search the optimization space based on accumulated experience. We then apply these methods to an example of monocentric lens design, and explore the improvement in system performance obtained through increasing the system volume.     

Nonequilibrium route to nanodiamond with astrophysical implications

Nanometer-sized diamond grains are commonly found in primitive chondritic meteorites, but their origin is puzzling. Using evidence from atomistic simulation, we establish a mechanism by which nanodiamonds form abundantly in space in a two-stage process involving condensation of vapor to form carbon onions followed by transformation to nanodiamond in an energetic impact. This nonequilibrium process is consistent with common environments in space and invokes the fewest assumptions of any proposed model. Accordingly, our model can explain nanodiamond formation in both presolar and solar environments. The model provides an attractive framework for understanding noble gas incorporation and explains all key features of meteoritic nanodiamond, including size, shape, and polytype. By understanding the creation of nanodiamonds, new opportunities arise for their exploitation as a powerful astrophysical probe.     

Water adsorption on SrTiO3(001): II. Water,water, everywhere

The role of water adsorption on Ti-rich SrTiO₃(001) surface reconstructions is studied. Density functional calculations with hybrid functionals of numerous adsorption configurations indicate that the relative stability of the different reconstructions is strongly altered by the addition of water, with all the reconstructions having comparable energy for half-monolayer coverage, most with a fair degree of hydrogen bonding. This strongly suggests that which reconstruction is observed depends upon a competition between the kinetics of ordering and dehydration. X-ray photoelectron spectra are consistent with the theoretical predictions for the dehydration of the 2 × 1 and c(4 × 2) reconstructions.     

Water adsorption on SrTiO3(001): I. Experimental and simulated STM

Density functional theory-based simulations of scanning tunneling micrographs were used for comparison to published experimental images of reconstructed SrTiO₃(001) surfaces. It was found that the addition of dissociatively adsorbed H₂O to the presently accepted structural solution of the 2 × 1 reconstruction is more consistent with the experimental data. A proposed model for the c(4 × 4) reconstruction, based on the hydrated 2 × 1 structure, agrees well with experiment and is consistent with a formation process consisting of the simple dehydration of a wet 2 × 1 structure.