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      Compact Shielding of Graphene Monolayer Leads to Extraordinary SERS-Active Substrate with Large-Area Uniformity and Long-Term Stability

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          Abstract

          Surface-enhanced Raman scattering (SERS) can significantly boost the inherently weak Raman scattering signal and provide detailed structural information and binding nature of the molecules on the surface. Despite the long history of this technology, SERS has yet to become a sophisticated analytical tool in practical applications. A major obstacle is the absence of high-quality and stable SERS-active substrate. In this work, we report a monolayer graphene-shielded periodic metallic nanostructure as large-area uniform and long-term stable SERS substrate. The monolayer graphene acting as a corrosion barrier, not only greatly enhanced stability, but also endowed many new features to the substrate, such as alleviating the photo-induced damages and improving the detection sensitivity for certain analytes that are weakly adsorbed on the conventional metallic substrates. Besides, our fabrication strategy were also capable of fabricating the reproducible SERS sensing spots array, which may serve as a promising high-throughput or multi-analyte sensing platform. Taken together, the graphene-shielded SERS substrate holds great promise both in fundamental studies of the SERS effect and many practical fields.

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          Most cited references27

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          Graphene: Status and Prospects

          A. K. Geim (2010)
          Graphene is a wonder material with many superlatives to its name. It is the thinnest material in the universe and the strongest ever measured. Its charge carriers exhibit giant intrinsic mobility, have the smallest effective mass (it is zero) and can travel micrometer-long distances without scattering at room temperature. Graphene can sustain current densities 6 orders higher than copper, shows record thermal conductivity and stiffness, is impermeable to gases and reconciles such conflicting qualities as brittleness and ductility. Electron transport in graphene is described by a Dirac-like equation, which allows the investigation of relativistic quantum phenomena in a bench-top experiment. What are other surprises that graphene keeps in store for us? This review analyses recent trends in graphene research and applications, and attempts to identify future directions in which the field is likely to develop.
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            Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils

            Graphene has been attracting great interest because of its distinctive band structure and physical properties. Today, graphene is limited to small sizes because it is produced mostly by exfoliating graphite. We grew large-area graphene films of the order of centimeters on copper substrates by chemical vapor deposition using methane. The films are predominantly single layer graphene with a small percentage (less than 5%) of the area having few layers, and are continuous across copper surface steps and grain boundaries. The low solubility of carbon in copper appears to help make this growth process self-limiting. We also developed graphene film transfer processes to arbitrary substrates, and dual-gated field-effect transistors fabricated on Si/SiO2 substrates showed electron mobilities as high as 4050 cm2V-1s-1 at room temperature.
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              Negligible particle-specific antibacterial activity of silver nanoparticles.

              For nearly a decade, researchers have debated the mechanisms by which AgNPs exert toxicity to bacteria and other organisms. The most elusive question has been whether the AgNPs exert direct "particle-specific" effects beyond the known antimicrobial activity of released silver ions (Ag(+)). Here, we infer that Ag(+) is the definitive molecular toxicant. We rule out direct particle-specific biological effects by showing the lack of toxicity of AgNPs when synthesized and tested under strictly anaerobic conditions that preclude Ag(0) oxidation and Ag(+) release. Furthermore, we demonstrate that the toxicity of various AgNPs (PEG- or PVP- coated, of three different sizes each) accurately follows the dose-response pattern of E. coli exposed to Ag(+) (added as AgNO(3)). Surprisingly, E. coli survival was stimulated by relatively low (sublethal) concentration of all tested AgNPs and AgNO(3) (at 3-8 μg/L Ag(+), or 12-31% of the minimum lethal concentration (MLC)), suggesting a hormetic response that would be counterproductive to antimicrobial applications. Overall, this work suggests that AgNP morphological properties known to affect antimicrobial activity are indirect effectors that primarily influence Ag(+) release. Accordingly, antibacterial activity could be controlled (and environmental impacts could be mitigated) by modulating Ag(+) release, possibly through manipulation of oxygen availability, particle size, shape, and/or type of coating.
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                Author and article information

                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group
                2045-2322
                30 November 2015
                2015
                : 5
                : 17167
                Affiliations
                [1 ]College of Biosystems Engineering and Food Science, Zhejiang University , Hangzhou 310058, China
                [2 ]State Key Laboratory of Modern Optical Instrumentation, College of Optical Science and Engineering, Zhejiang University , Hangzhou 310027, China
                [3 ]Institute of Microelectronics and Optolectronics, Zhejiang University , Hangzhou 310027, China
                Author notes
                Article
                srep17167
                10.1038/srep17167
                4663485
                26617190
                794be410-8425-4c5b-984f-0aa13aeb5550
                Copyright © 2015, Macmillan Publishers Limited

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 10 April 2015
                : 16 September 2015
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