Chemically isolating hot spots on concave nanocubes

The article of record as published may be found at http://dx.doi.org/10.1021/nl3032235We report a simple and general strategy for selectively exposing and functionalizing the sharp corners of concave nanocubes, which are the SERS hot spots for such structures. This strategy takes advantage of the unique shape of the concave cubes by coating the particles with silica and then etching it away to expose only the corner regions, while maintaining the silica coating in the concave faces. These corner regions can then be selectively modified for improved enhancement and signal response with SERSFunded by Naval Postgraduate School.AFOSRNational Science FoundationNERC (DOE)Awards No. N00244-09-1-0012 and N00244-09-1-0071 (NPS)Award no. FA9550-09-1-0294 (AFOSR)DMR-0520513 and DMR-01121262 (NSF)Award no. DE-SC0000989 (NERC

Design of template-stabilized active and earth-abundant oxygen evolution catalysts in acid† †Electronic supplementary information (ESI) available: CVs for unary metal oxides deposition, electrochemical stability at higher current densities for unary metal oxides at pH 2.5, EDS maps for CoMnOx and CoPbOx, STEM images and PXRD of CoMnOx and CoFePbOx, high-resolution XPS of Fe 2p for CoFePbOx, Pourbaix diagrams (of Mn, Co, Pb, and Fe), and elemental analysis. See DOI: 10.1039/c7sc01239j Click here for additional data file.

Oxygen evolution reaction (OER) catalysts that are earth-abundant and are active and stable in acid are unknown. Active catalysts derived from Co and Ni oxides dissolve at low pH, whereas acid stable systems such as Mn oxides (MnOx) display poor OER activity. We now demonstrate a rational approach for the design of earth-abundant catalysts that are stable and active in acid by treating activity and stability as decoupled elements of mixed metal oxides. Manganese serves as a stabilizing structural element for catalytically active Co centers in CoMnOx films. In acidic solutions (pH 2.5), CoMnOx exhibits the OER activity of electrodeposited Co oxide (CoOx) with a Tafel slope of 70–80 mV per decade while also retaining the long-term acid stability of MnOx films for OER at 0.1 mA cm–2. Driving OER at greater current densities in this system is not viable because at high anodic potentials, Mn oxides convert to and dissolve as permanganate. However, by exploiting the decoupled design of the catalyst, the stabilizing structural element may be optimized independently of the Co active sites. By screening potential–pH diagrams, we replaced Mn with Pb to prepare CoFePbOx films that maintained the high OER activity of CoOx at pH 2.5 while exhibiting long-term acid stability at higher current densities (at 1 mA cm–2 for over 50 h at pH 2.0). Under these acidic conditions, CoFePbOx exhibits OER activity that approaches noble metal oxides, thus establishing the viability of decoupling functionality in mixed metal catalysts for designing active, acid-stable, and earth-abundant OER catalysts

Respiratory Health Symptoms among Students Exposed to Different Levels of Air Pollution in a Turkish City

In this study, we aimed to investigate the frequency of respiratory health symptoms among high school students attending schools at industrial, urban and rural areas in a Turkish city. Three schools located in different zones of the city having different pollution characteristics were chosen based on the pollutant distribution maps using Geographical Information Systems (GIS) software. A cross-sectional survey was performed among 667 high school students in the schools. Outdoor and indoor nitrogen dioxide (NO2) and ozone (O-3) concentrations were also measured by passive samplers in the same schools to investigate possible routes of exposure. Chronic pulmonary disease (OR = 1.49; 95% CI: 1.11-1.99; p = 0.008), tightness in the chest (OR = 1.57; 95% CI: 1.22-2.02; p = 0.001), morning cough (OR = 1.81 95% CI: 1.19-2.75; p = 0.006) were higher among students in the industrial zone where nitrogen dioxide and ozone levels were also highest. There were no indoor sources of nitrogen dioxide and ozone exists in the schools except for the dining hall. As a conclusion, this study has noticed that air pollution and respiratory health problems among high school students are high in industrial zones and the use of passive samplers combined with GIS is an effective tool that may be used by public health researchers to identify pollutant zones and persons at risk

The role of amifostine on late normal tissue damage induced by pelvic radiotherapy with concomitant gemcitabine: an in vivo study

13th European Cancer Conference (ECCO 13) -- OCT 30-NOV 03, 2005 -- Paris, FRANCEWOS: 000272045400004PubMed ID: 19043677In this in vivo study, we aimed to assess the radioprotective effect of amifostine on late normal tissue damage induced by gemcitabine concomitant with pelvic radiotherapy by histopathological and quantitative methods. Fifty-six male Wistar albino rats were randomly divided into seven experimental groups as follows: (I) gemcitabine, (II) radiation + gemcitabine, (III) radiation + gemcitabine + amifostine, (IV) radiation + amifostine, (V) sham radiation, (VI) amifostine, (VII) radiation. Irradiation was given to pelvic region with a dose of 25 Gy in 5 fractions. Amifostine was given for 30 min; gemcitabine was administered 24 h before the first fraction of radiotherapy. All animals were killed at the end of 4th month. Pathological examination was performed and the tissue collagen content was measured in bladder and rectal tissues. Fifty-one animals that were alive at the end of the follow-up period were analyzed. Thirty-five animals (68.6%) revealed grades I-III late effect in histopathological examination. We observed grade III colitis in 1 animal (radiation + gemcitabine) and bladder fibrosis in 4 animals (radiation and radiation + gemcitabine groups). There was no significant difference between any groups for bladder cystitis and fibrosis by Kruskal-Wallis method. Colitis was seen significantly lower in the radiation + gemcitabine + amifostine group (P = 0.0005). The collagen contents in the bladder and rectum of radiation and radiation + gemcitabine groups were markedly increased as compared to the sham group. This effect was reversed in the groups which received amifostine in addition to radiation and radiation + gemcitabine groups, but this difference was not significant. This study demonstrated that amifostine may have a beneficial effect in limiting rectal colitis from the radiosensitizing effect of gemcitabine

Chemically Isolating Hot Spots on Concave Nanocubes

We report a simple and general strategy for selectively exposing and functionalizing the sharp corners of concave nanocubes, which are the SERS hot spots for such structures. This strategy takes advantage of the unique shape of the concave cubes by coating the particles with silica and then etching it away to expose only the corner regions, while maintaining the silica coating in the concave faces. These corner regions can then be selectively modified for improved enhancement and signal response with SERS

Systematic Study of Antibonding Modes in Gold Nanorod Dimers and Trimers

Using on-wire lithography to synthesize well-defined nanorod dimers and trimers, we report a systematic study of the plasmon coupling properties of such materials. By comparing the dimer/trimer structures to discrete nanorods of the same overall length, we demonstrate many similarities between antibonding coupled modes in the dimers/trimers and higher-order resonances in the discrete nanorods. These conclusions are validated with a combination of discrete dipole approximation and finite-difference time-domain calculations and lead to the observation of antibonding modes in symmetric structures by measuring their solution-dispersed extinction spectra. Finally, we probe the effects of asymmetry and gap size on the occurrence of these modes and demonstrate that the delocalized nature of the antibonding modes lead to longer-range coupling compared to the stronger bonding modes