A Functionalized Ag2S Molecular Architecture: Facile Assembly of the Atomically Precise Ferrocene‐Decorated Nanocluster [Ag74S19(dppp)6(fc(C{O}OCH2CH2S)2)18]

A ferrocene‐based dithiol 1,1′‐[fc(C{O}OCH₂CH₂SH)₂] has been prepared and treated with a Ag^I salt to form the stable dithiolate compound [fc(C{O}OCH₂CH₂SAg)₂]_n (fc=[Fe(η⁵‐C₅H₄)₂]). This is used as a reagent for the preparation of the nanocluster [Ag₇₄S₁₉(dppp)₆(fc(C{O}OCH₂CH₂S)₂)₁₈] which was obtained in good yield (dppp=1,3‐bis(diphenylphosphino)propane).     

High Ethene/Ethane Selectivity in 2,2′‐Bipyridine‐Based Silver(I) Complexes by Removal of Coordinated Solvent

Following removal of coordinated CH₃CN, the resulting complexes [Ag^I(2,2′‐bipyridine)][BF₄] ( 1 ) and [Ag^I(6,6′‐dimethyl‐2,2′‐bipyridine)][OTf] ( 2 ) show ethene/ethane sorption selectivities of 390 and 340, respectively, and corresponding ethene sorption capacities of 2.38 and 2.18 mmol g^?1 when tested at an applied gas pressure of 90 kPa and a temperature of (20±1) °C. These ethene/ethane selectivities are 13 times higher than those reported for known solid sorbents for ethene/ethane separation. For 2 , ethene sorption reached 90 % of equilibrium capacity within 15 minutes, and this equilibrium capacity was maintained over the three sorption/desorption cycles tested. The rates of ethene sorption were also measured. To our knowledge, these are the first complexes, designed for olefin/paraffin separations, which have open silver(I) sites. The high selectivities arise from these open silver(I) sites and the relatively low molecular surface areas of the complexes.     

A facile method for the synthesis of large‐size Ag nanoparticles as efficient SERS substrates

Silver nanoparticles (Ag NPs) enjoy a reputation as an ultrasensitive substrate for surface‐enhanced Raman spectroscopy (SERS). However, large‐scale synthesis of Ag NPs in a controlled manner is a challenging task for a long period of time. Here, we reported a simple seed‐mediated method to synthesize Ag NPs with controllable sizes from 50 to 300 nm, which were characterized by scanning electron microscopy (SEM) and UV–Vis spectroscopy. SERS spectra of Rhodamine 6G (R6G) from the as‐prepared Ag NPs substrates indicate that the enhancement capability of Ag NPs varies with different excitation wavelengths. The Ag NPs with average sizes of ~150, ~175, and ~225 nm show the highest SERS activities for 532, 633, and 785‐nm excitation, respectively. Significantly, 150‐nm Ag NPs exhibit an enhancement factor exceeding 10⁸ for pyridine (Py) molecules in electrochemical SERS (EC‐SERS) measurements. Furthermore, finite‐difference time‐domain (FDTD) calculation is employed to explain the size‐dependent SERS activity. Finally, the potential of the as‐prepared SERS substrates is demonstrated with the detection of malachite green. Copyright © 2016 John Wiley & Sons, Ltd.     

Raman spectroscopic probing of plant material using SERS

We report surface‐enhanced Raman studies on intact plant material using onion layers as a biological target, and silver nanoaggregates and silver island films as enhancing plasmonic structures. Surface‐enhanced Raman scattering (SERS) enhancement allows the detection of strong Raman signatures of chemical constituents of the surface of the onion layer such as cellulose, proteins, and flavonols. Because of long‐time incubation, SERS sensors can access the extracellular space in the inner of the layer. The location of silver nanoparticles inside the onion layer has been monitored by the SERS images collected from chemicals present in the onion and/or reporter molecules attached to the nanoparticles. Our studies show a competitive adsorption of intrinsic bio molecules of the onion layer and reporter molecules. Different spectra from different places of the layer indicate the complex heterogeneous chemical structure of the plant material. The pH‐sensitive reporter molecule para mercapto benzoic acid attached to the nanoparticles allows us to infer pH values inside the extracellular matrix of the onion layer. Copyright © 2015 John Wiley & Sons, Ltd.     

Plasmonic refraction‐induced ultrahigh transparency of highly conducting metallic networks

We demonstrate a high optoelectronic performance and application potential of our random network, with subwavelength diameter, ultralong, and high‐quality silver nanowires, stabilized on a substrate with a UV binder. Our networks show very good optoelectronic properties, with the single best figure of merit of ∼1686, and excellent stability under harsh mechanical strain, as well as thermal, and chemical challenge. Our network transparency strongly exceeds the simple shading limit. We show that this transmission enhancement is due to plasmonic refraction, which in an effective medium picture involves localized plasmons, and identify the inhomogeneous broadening as the key factor in promoting this mechanism. Such networks could become a basis for a next generation of ultrahigh‐performance transparent conductors.

     

Polymer-Nanoparticle Composites Composed of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and Coated Silver Nanoparticles

The effects of addition of synthesized organic-suspension silver nanoparticles on the crystallization and thermal stability of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) were studied by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (XRD), UV-Vis absorption spectroscopy, polarized optical microscopy (POM), and thermal gravimetric analysis (TGA). The TEM images showed the average primary size of the as-synthesized silver nanoparticles, coated with a monolayer of the surfactants consisting of oleic acid and an alkylamine, was about 5 nm with narrow distribution, and that they were uniformly dispersed in n-heptane. PHBV/silver nanocomposites were prepared by melt mixing in an internal mixer and then injection molded into rectangle-shaped specimens by a labscale injection molding device. The coated silver nanoparticles showed a homogenuous dispersion in the PHBV matrix when the content of coated silver nanoparticles was about 1%. Both the DSC and POM data showed the efficient heterogeneous nucleation by the coated silver nanoparticles for facilitating PHBV crystallization. The thermal stability of the PHBV/silver nanocomposites improved with the increase in the content of the coated silver nanoparticles.     

银纳米颗粒/多孔硅复合材料的制备与气敏性能研究

采用双槽电化学腐蚀法以电阻率为10-15 Ω·cm的p型<100>晶向的单晶硅片制备了孔径约为1.5 μm, 孔深约为15-20 μm的p型多孔硅, 并以此多孔硅作为基底采用无电沉积法通过调控沉积时间在其表面沉积了不同厚度的银纳米颗粒薄膜. 采用扫描电子显微镜和X 射线衍射仪表征了银纳米颗粒/多孔硅复合材料的形貌和微观结构, 结果表明银纳米颗粒较均匀的分布于多孔硅的表面上且沉积时间对产物的形貌有重要影响. 采用静态配气法在室温下研究了银纳米颗粒/多孔硅复合材料对NH₃的气敏性能. 气敏测试结果表明沉积时间对产物的气敏性能影响较大. 当沉积时间较短时, 适量银纳米颗粒掺杂的多孔硅复合材料由于其较高的比表面积以及特殊的形貌和结构, 对NH₃气体表现出较高的灵敏度、优良的响应/恢复性能. 室温下, 其对50 ppm 的NH₃气体的气敏灵敏度可以达到5.8左右.     

十字结构银纳米线的表面等离极化激元分束特性

金属纳米线波导可以将光局域在亚波长尺度内传播, 在纳米光子集成回路方面有着重要的作用. 本文应用有限元方法, 研究了十字结构银纳米线的表面等离极化激元分束特性. 结果表明, 不同模式的表面等离极化激元在十字结构三个分支的输出依赖于端面的几何结构参数. 此外, 研究还发现由于不同模式表面等离极化激元叠加, 在十字结构的分支上出现了周期性电场分布.     

Discovery of radioactive silver (110mAg) in spiders and other fauna in the terrestrial environment after the meltdown of Fukushima Dai-ichi nuclear power plant

Six months after the explosion of TEPCO’s Fukushima Dai-ichi nuclear power plant, radioactive silver (^110mAg), was detected in concentrations of 3754 Bq/kg in Nephila clavata (the orb-web spider; Joro-gumo in Japanese) collected at Nimaibashi, Iitate village in Fukushima Prefecture, whereas ^110mAg in the soil was 43.1 Bq/kg. A survey of 35 faunal species in the terrestrial environment during the 3.5 years after the accident showed that most of Anthropoda had two orders higher ^110mAg in their tissues than soils, although silver is not an essential element for their life. However, tracing of the activity of ^110mAg detected in spider Atypus karschi collected regularly at a fixed location showed that it declined much faster than the physical half-life. These results suggest that ^110mAg was at once biologically concentrated by faunal species, especially Arthropoda, through food chain. The factors affecting the subsequent rapid decline of ^110mAg concentration in faunal species are discussed.