Low Vapor Pressure Solvents for Single-Molecule Junction Measurements.

Nonpolar solvents commonly used in scanning tunneling microscope-based break junction measurements exhibit hazards and relatively low boiling points (bp) that limit the scope of solution experiments at elevated temperatures. Here we show that low toxicity, ultrahigh bp solvents such as bis(2-ethylhexyl) adipate (bp = 417 °C) and squalane (457 °C) can be used to probe molecular junctions at ≥100 °C. With these, we extend solvent- and temperature-dependent conductance trends for junction components such as 4,4'-bipyridine and thiomethyl-terminated oligophenylenes and reveal the gold snapback distance is larger at 100 °C due to increased surface atom mobility. We further show the rate of surface transmetalation and homocoupling reactions using phenylboronic acids increases at 100 °C, while junctions comprising anticipated boroxine condensation products form only at room temperature in an anhydrous glovebox atmosphere. Overall, this work demonstrates the utility of low vapor pressure solvents for the comprehensive characterization of junction properties and chemical reactivity at the single-molecule limit.

Optimized film processing of nanosilver colloids for photoluminescence enhancement.

Recently, various research strategies have been employed to improve light extraction efficiency in organic LEDs, including the recent development of localized surface plasmon resonance (LSPR), as well as the more widely-known application of a photonic crystal layer. Here, we report on the development of a process method for forming a two-dimensional nanosilver patterned array to achieve LSPR-coupled light-emission efficiency enhancement. The process scheme involves the spin-coating of nanosilver colloidal ink onto a glass substrate, followed by optimized thermal annealing to create an array of isolated nanosilver islands. The resulting Ag islands are in the size range 50 approximately 80 nm, which is larger than the diameter of the Ag nanoparticles in the colloidal suspension. Then, silicon oxide is thermally sputtered to provide a spacer layer to prevent luminescence quenching of the red-emitting nanocrystal quantum dot (NQD) layer, which is deposited in a subsequent spin-coating process. When the NQD layer is excited, the energy of the photoelectron is confined to the surfaces of the nanosilver islands in the near-field. In this study, the localized surface plasmon resonance peaks were at a wavelength of 625 nm, and out-coupling efficiency was enhanced more than sixfold.

Continuous-Wave Laser-Induced Transfer of Metal Nanoparticles to Arbitrary Polymer Substrates.

Laser-induced forward transfer (LIFT) and selective laser sintering (SLS) are two distinct laser processes that can be applied to metal nanoparticle (NP) ink for the fabrication of a conductive layer on various substrates. A pulsed laser and a continuous-wave (CW) laser are utilized respectively in the conventional LIFT and SLS processes; however, in this study, CW laser-induced transfer of the metal NP is proposed to achieve simultaneous sintering and transfer of the metal NP to a wide range of polymer substrates. At the optimum laser parameters, it was shown that a high-quality uniform metal conductor was created on the acceptor substrate while the metal NP was sharply detached from the donor substrate, and we anticipate that such an asymmetric transfer phenomenon is related to the difference in the adhesion strengths. The resultant metal electrode exhibits a low resistivity that is comparable to its bulk counterpart, together with strong adhesion to the target polymer substrate. The versatility of the proposed process in terms of the target substrate and applicable metal NPs brightens its prospects as a facile manufacturing scheme for flexible electronics.

Quantitative mass spectrometric analysis of the mouse cerebral cortex after ischemic stroke.

Ischemic strokes result in the death of brain tissue and a wave of downstream effects, often leading to lifelong disabilities or death. However, the underlying mechanisms of ischemic damage and repair systems remain largely unknown. In order to better understand these mechanisms, TMT-isobaric mass tagging and mass spectrometry were conducted on brain cortex extracts from mice subjected to one hour of middle cerebral artery occlusion (MCAO) and after one hour of reperfusion. In total, 2,690 proteins were identified and quantified, out of which 65% of the top 5% of up- and down-regulated proteins were found to be significant (p < 0.05). Network-based gene ontology analysis was then utilized to cluster all identified proteins by protein functional groups and cellular roles. Although three different cellular functions were identified-organelle outer membrane proteins, cytosolic ribosome proteins, and spliceosome complex proteins-several functional domains were found to be common. Of these, organelle outer membrane proteins were downregulated whereas cytosolic ribosome and spliceosome complex proteins were upregulated, indicating that major molecular events post-stroke were translation-associated and subsequent signaling pathways (e.g., poly (ADP-ribose) (PAR) dependent cell death). By approaching stroke analyses via TMT-isobaric mass tagging, the work herein presents a grand scope of protein-based molecular mechanisms involved with ischemic stroke recovery.

Characteristics of Carrier Collection of Nanopillar-Patterned Silicon Solar Cells.

Nanopillar-patterned Si solar cells were investigated. Ag nanoparticles were coated on a polished Si substrate as an etching mask. Reactive ion etching caused Si nanopillars to replicate in a reverse fashion on the Ag nanoparticles over a large area. The nanopillar structures efficiently reduced the light reflection on the surface and effectively drove the incident light into a Si absorber. This induced a significant enhancement of the photogenerated-current with an improved solar cell efficiency of 16.07%. The Si nanopillar-patterned solar cells showed improved carrier collection for long wavelengths; however, the surface-defect induced recombination degraded the quantum efficiency at short wavelengths. We suggest that the reduction of recombination loss should be considered for efficient nanostructure solar cells.

An Antireflective Nanostructure Array Fabricated by Nanosilver Colloidal Lithography on a Silicon Substrate.

An alternative method is presented for fabricating an antireflective nanostructure array using nanosilver colloidal lithography. Spin coating was used to produce the multilayered silver nanoparticles, which grew by self-assembly and were transformed into randomly distributed nanosilver islands through the thermodynamic action of dewetting and Oswald ripening. The average size and coverage rate of the islands increased with concentration in the range of 50-90 nm and 40-65%, respectively. The nanosilver islands were critically affected by concentration and spin speed. The effects of these two parameters were investigated, after etching and wet removal of nanosilver residues. The reflection nearly disappeared in the ultraviolet wavelength range and was 17% of the reflection of a bare silicon wafer in the visible range.

Nanosilver Colloids-Filled Photonic Crystal Arrays for Photoluminescence Enhancement.

For the improved surface plasmon-coupled photoluminescence emission, a more accessible fabrication method of a controlled nanosilver pattern array was developed by effectively filling the predefined hole array with nanosilver colloid in a UV-curable resin via direct nanoimprinting. When applied to a glass substrate for light emittance with an oxide spacer layer on top of the nanosilver pattern, hybrid emission enhancements were produced from both the localized surface plasmon resonance-coupled emission enhancement and the guided light extraction from the photonic crystal array. When CdSe/ZnS nanocrystal quantum dots were deposited as an active emitter, a total photoluminescence intensity improvement of 84% was observed. This was attributed to contributions from both the silver nanoparticle filling and the nanoimprinted photonic crystal array.