Controlling inelastic light scattering quantum pathways in graphene.

Inelastic light scattering spectroscopy has, since its first discovery, been an indispensable tool in physical science for probing elementary excitations, such as phonons, magnons and plasmons in both bulk and nanoscale materials. In the quantum mechanical picture of inelastic light scattering, incident photons first excite a set of intermediate electronic states, which then generate crystal elementary excitations and radiate energy-shifted photons. The intermediate electronic excitations therefore have a crucial role as quantum pathways in inelastic light scattering, and this is exemplified by resonant Raman scattering and Raman interference. The ability to control these excitation pathways can open up new opportunities to probe, manipulate and utilize inelastic light scattering. Here we achieve excitation pathway control in graphene with electrostatic doping. Our study reveals quantum interference between different Raman pathways in graphene: when some of the pathways are blocked, the one-phonon Raman intensity does not diminish, as commonly expected, but increases dramatically. This discovery sheds new light on the understanding of resonance Raman scattering in graphene. In addition, we demonstrate hot-electron luminescence in graphene as the Fermi energy approaches half the laser excitation energy. This hot luminescence, which is another form of inelastic light scattering, results from excited-state relaxation channels that become available only in heavily doped graphene.

Monitoring Telomere Maintenance During Regeneration of Annelids.

Telomere shortening is a hallmark of aging and eventually constrains the proliferative capacity of cells. The protocols discussed here are used for monitoring telomeres comprehensively in Aeolosoma viride, a model system for regeneration studies. We present methods for analyzing the activity of telomerase enzyme in regenerating tissue by telomeric repeat amplification protocol (TRAP) assay, for comparing telomere length between existing tissue and newly regenerated tissue by telomere restriction fragment (TRF) assay, as well as for visualizing telomeres by fluorescence in situ hybridization (FISH).

Multilength-scale chemical patterning of self-assembled monolayers by spatially controlled plasma exposure: nanometer to centimeter range.

We present a generic and efficient chemical patterning method based on local plasma-induced conversion of surface functional groups on self-assembled monolayers (SAMs). Here, spatially controlled plasma exposure is realized by elastomeric poly(dimethylsiloxane) (PDMS) contact masks or channel stamps with feature sizes ranging from nanometer, micrometer, to centimeter. This chemical conversion method has been comprehensively characterized by a set of techniques, including contact angle measurements, X-ray photoelectron spectroscopy (XPS), scanning photoelectron microscopy (SPEM), scanning electron microscopy (SEM), and scanning Kelvin probe microscopy (SKPM). In particular, XPS and SPEM can be used to distinguish regions of different surface functionalities and elucidate the mechanism of plasma-induced chemical conversion. In the case of an octadecyltrichlorosilane (OTS) monolayer, we show that exposure to low-power air plasma causes hydroxylation and oxidation of the methyl terminal group on an OTS-covered Si surface and generates polar functional groups such as hydroxyl, aldehylde, and carboxyl groups, which can allow subsequent grafting of dissimilar SAMs and adsorption of colloid nanoparticles onto the patterned areas with an achievable resolution down to the 50 nm range.

Tunable plasmonic response from alkanethiolate-stabilized gold nanoparticle superlattices: evidence of near-field coupling.

We report on the self-assembly of large-area, highly ordered 2D superlattices of alkanethiolate-stabilized gold nanoparticles ( approximately 10.5 nm in core diameter) onto quartz substrates with varying lattice constants, which can be controlled by the alkyl chain lengths, ranging from C12 (1-dodecanethiolate), C14 (1-tetradecanethiolate), C16 (1-hexadecanethiolate), to C18 (1-octadecanethiolate). These 2D nanoparticle superlattices exhibit strong collective surface plasmon resonance that is tunable via the near-field coupling of adjacent nanoparticles. The approach presented here provides a unique and viable means of building artificial "plasmonic crystals" with precisely designed optical properties, which can be useful for the emerging fields of plasmonics, such as subwavelength integrated optics.

Telomere maintenance during anterior regeneration and aging in the freshwater annelid Aeolosoma viride.

Aging is a complex process involving declines in various cellular and physical functionalities, including regenerative ability. Telomere maintenance is thought to be necessary for regeneration, and telomere attrition is one mechanism that contributes to aging. However, it is unclear if aging affects regeneration owing to deterioration of telomeric maintenance. We introduce Aeolosoma viride-a freshwater annelid with strong regenerative abilities-as a new model for studying the effects of aging on telomere functions and regeneration. We show that the anterior regenerative ability of A. viride declines with age. We characterized the A. viride telomere sequence as being composed of TTAGGG repeats and identifyied the telomerase gene Avi-tert. In adult A. viride, telomerase was constantly active and telomere lengths were similar among different body sections and stably maintained with age. Notably, we found that regeneration did not result in telomere shortening at regenerating sites. Moreover, transient up-regulation of Avi-tert expression and telomerase activity was observed at regenerating sites, which might promote telomere lengthening to counteract telomere erosion resulting from cell proliferation. Our study suggests that although aging affects A. viride regeneration independent of steady-state telomere length, timely regulation of telomerase functions is critical for the regeneration process in A. viride.

Integrated chemical species analysis with source-receptor modeling results to characterize the effects of terrain and monsoon on ambient aerosols in a basin.

This study integrated estimated oxidation ratio of sulfur (SOR) and oxidation ratio of nitrogen (NOR) with source-receptor modeling results to identify the effects of terrain and monsoons on ambient aerosols in an urban area (north basin) and a rural area (south basin) of the Taichung Basin. The estimated results indicate that the conversion of sulfur mainly occurs in fine particles (PM2.5), whereas the conversion of nitrogen occurs in approximately equal quantities of PM2.5 and coarse particles (PM2.5-10). The results show a direct relationship for PM2.5 between the modeling results with SOR and NOR. The high PM2.5 SOR, NOR, and secondary aerosol values all occurred in the upwind area during both monsoons; this shows that the photochemical reaction and the terrain effect on the pollutant transmission were significant in the basin. Additionally, the urban heat island effect on the urban area and the valley effect on the rural area were significant. The results show that secondary aerosol in PM2.5-10 contributed approximately 10 % during both monsoons, and the difference in the contribution from secondary aerosol between both areas was small. Vehicle exhaust emissions and wind-borne dust were two crucial PM2.5-10 contributors during both monsoons; their average contributions in both areas were higher than 34 and 32 %, respectively.

Using a source-receptor approach to characterize the volatile organic compounds from control device exhaust in a science park.

The science parks have helped shape Taiwan as a high-tech island with a good reputation worldwide. But some complaints on air pollution from the science parks have recently risen. To better understand the environmental effects of volatile organic compounds (VOCs) emitted from various high-tech factories in a science park, this study uses a source-receptor approach to characterize the environmental effects of VOCs from control device exhaust in Taichung Science Park. The chemical mass balance model (CMB8.2) of field measurements of 30 stacks and ambient air at nine sites was used to identify the source and relative contribution of ambient VOCs. The exhaust gas of various pollution control devices was also sampled by drawing a stream of the gases from the exhaust duct at its sampling port. The VOC source profile of each control device exhaust was determined using a database of noncharacteristic compounds. Monthly ambient concentrations of 167 VOCs were divided into monsoon datasets to investigate the effect of monsoon conditions on the emission of VOCs in the science park. This study also suggests a method for determining the optimum source profile in source-receptor modeling, and identifies and analyzes the sources of ambient VOCs at nine sites during southwest and northeast monsoons. Results show a direct relationship between the relative contribution of each source and its control device efficiency. The proposed source-receptor approach can characterize the environmental effect of air pollutants from various factories and successfully assess the efficiency of various control devices.

Rice BGlu1 glycosynthase and wild type transglycosylation activities distinguished by cyclophellitol inhibition.

The rice BGlu1 ß-D-glucosidase nucleophile mutant E386G is a glycosynthase that catalyzes the synthesis of cellooligosaccharides from α-d-glucopyranosyl fluoride (GlcF) donor and p-nitrophenyl (pNP) cellobioside (Glc2-pNP) or cello-oligosaccharide acceptors. When activity with other donors and acceptors was tested, the initial enzyme preparation cleaved pNP-ß-D-glucopyranoside (Glc-pNP) and pNP-ß-D-fucopyranoside (Fuc-pNP) to pNP and glucose and fucose, suggesting contamination with wild type BGlu1 ß-glucosidase. The products from reaction of GlcF and Fuc-pNP included Fuc-ß-(1→3)-Fuc-pNP, Glc-ß-(1→3)-Fuc-pNP, and Fuc-ß-(1→4)-Glc-ß-(1→3)-Fuc-pNP, suggesting the presence of both wild type BGlu1 and its glycosynthase. Inhibition of the BGlu1 ß-glucosidase activity within this preparation by cyclophellitol confirmed that the E386G glycosynthase preparation was contaminated with wild type BGlu1. Rice BGlu1 E386G-2, generated from a new construct designed to minimize back-mutation, showed glycosynthase activity without wild type hydrolytic or transglycosylation activity. E386G-2 catalyzed transfer of glycosyl residues from GlcF, α-L-arabinosyl fluoride, α-D-fucosyl fluoride, α-D-galactosyl fluoride, α-D-mannosyl fluoride, and α-D-xylosyl fluoride donors to Glc2-pNP acceptor. The synthetic products from the reactions of α-fucosyl fluoride and α-mannosyl fluoride donors were confirmed to result from addition of a ß-(1→4)-linked glycosyl residue. Moreover, the E386G glycosynthase transferred glucose from GlcF donor to glucose, cellobiose, Glc-pNP, Fuc-pNP, pNP-ß-D-galactopyranoside, and pNP-ß-D-xylopyranoside acceptors, but little to pNP-ß-D-mannopyranoside. Production of longer oligosaccharides occurred most readily on acceptors with an equatorial 4-OH. Elimination of wild type contamination thereby allowed a clear assessment of BGlu1 E386G glycosynthase catalytic abilities.

Electrostatic assembly of gold colloidal nanoparticles on organosilane monolayers patterned by microcontact electrochemical conversion.

A new approach is introduced for electrostatically guided adsorption of colloidal nanoparticles onto a patterned self-assembled monolayer (SAM) with feature sizes ranging from nm to mm. Patterning of the adsorption templates is realized by electric-field-induced anodic oxidation of aminosilane SAM using an ink-free method. In this versatile method, both "positive" and "negative" type pattern transfers are possible. The chemically converted patterns are induced by localized electrical fields on the microcontacted areas, and the patterning resolution is insensitive to the diffusion of oxidizing agents because of the self-limiting oxidation kinetics, thereby enabling high-resolution, large-scale parallel patterning.