Breaking the diffusion limit with super-hydrophobic delivery of molecules to plasmonic nanofocusing SERS structures

Angelis, Francesco De; Gentile, Francesco; Mecarini, Federico; Das, Gobind; Moretti, Manola; Candeloro, Patrizio; Coluccio, Maria Laura; Cojoc, Gheorghe; Accardo, Angelo; Liberale, Carlo; Zaccaria, Remo Proietti; Perozziello, Gerardo; Tirinato, Luca; Toma, Andréa; Cuda, Giovanni; Cingolani, R.; Fabrizio, E. Di

doi:10.1038/nphoton.2011.222

Cited by 666 publications

(626 citation statements)

References 42 publications

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“…Optical nanoantennas have already been reported for the detection of analytes in solution [11] and of inorganic gases. [12] In the case of inorganic gases, these approaches rely on the fabrication of segregated alloys containing silver or gold as the optically active material and another metal (usually platinum or palladium) as the capture material.…”

Section: Methodsmentioning

confidence: 99%

Macroscale Plasmonic Substrates for Highly Sensitive Surface‐Enhanced Raman Scattering

et al. 2013

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Section: Methodsmentioning

confidence: 99%

Macroscale Plasmonic Substrates for Highly Sensitive Surface‐Enhanced Raman Scattering

et al. 2013

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“…Among various analytical techniques, surface-enhanced Raman scattering (SERS) is among the most promising methods in detecting trace amounts of molecules owing to its high molecular specificity (i.e., differentiation between different types of molecules) and high sensitivity (i.e., the lowest analyte concentration from which SERS signals are distinguishable from the noise signal of a control sample) (9)(10)(11)(12)(13)(14)(15)(16)(17). Extensive studies have focused on the structural optimization of the SERS substrate to improve SERS sensitivity (18)(19)(20)(21)(22), but there are two important roadblocks that limit its practical applications.…”

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confidence: 99%

“…Second, many real-life analytes such as environmental contaminants and explosives may be dispersed in liquid or gas phases or may be bound to solid substrates (e.g., soil), which may require the use of nonaqueous solvents for extraction. Various approaches have been explored to improve SERS sensitivity in aqueous solvents (16,28,29). Among them, using superhydrophobic surfaces to overcome the "diffusion limit" of analytes in highly diluted aqueous solutions is the most successful technique (16).…”

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confidence: 99%

Ultrasensitive surface-enhanced Raman scattering detection in common fluids

Yang

Dai

Stogin

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

634

442

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Detecting target analytes with high specificity and sensitivity in any fluid is of fundamental importance to analytical science and technology. Surface-enhanced Raman scattering (SERS) has proven to be capable of detecting single molecules with high specificity, but achieving single-molecule sensitivity in any highly diluted solutions remains a challenge. Here we demonstrate a universal platform that allows for the enrichment and delivery of analytes into the SERSsensitive sites in both aqueous and nonaqueous fluids, and its subsequent quantitative detection of Rhodamine 6G (R6G) down to ∼75 fM level (10 −15 mol·L −1 ). Our platform, termed slippery liquidinfused porous surface-enhanced Raman scattering (SLIPSERS), is based on a slippery, omniphobic substrate that enables the complete concentration of analytes and SERS substrates (e.g., Au nanoparticles) within an evaporating liquid droplet. Combining our SLIPSERS platform with a SERS mapping technique, we have systematically quantified the probability, p(c), of detecting R6G molecules at concentrations c ranging from 750 fM (p > 90%) down to 75 aM (10 −18 mol·L −1 ) levels (p ≤ 1.4%). The ability to detect analytes down to attomolar level is the lowest limit of detection for any SERS-based detection reported thus far. We have shown that analytes present in liquid, solid, or air phases can be extracted using a suitable liquid solvent and subsequently detected through SLIPSERS. Based on this platform, we have further demonstrated ultrasensitive detection of chemical and biological molecules as well as environmental contaminants within a broad range of common fluids for potential applications related to analytical chemistry, molecular diagnostics, environmental monitoring, and national security.spectroscopy | sensing | SERS | slippery surfaces | nanoparticles

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“…29,62 At t = 0, a droplet is in the equilibrium and the contact line is fixed. Then water starts to evaporate and therefore the droplet volume is continuously decreasing, which results in a decrease in the contact angle.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Robust Cassie State of Wetting in Transparent Superhydrophobic Coatings

Tuvshindorj

Yıldırım

Öztürk

et al. 2014

ACS Appl. Mater. Interfaces

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This paper investigates the stability of the Cassie state of wetting in transparent superhydrophobic coatings by comparing a single-layer microporous coating with a doublelayer micro/nanoporous coating. Increasing pressure resistance of superhydrophobic coatings is of interest for practical use because high external pressures may be exerted on surfaces during operation. The Cassie state stability against the external pressure of coatings was investigated by squeezing droplets sitting on surfaces with a hydrophobic plate. Droplets on the single-layer coating transformed to the Wenzel state and pinned to the surface after squeezing, whereas droplets on the double-layer micro/nanoporous coating preserved the Cassie state and rolled off the surface easily. In addition, the contact angle and contact-line diameter of water droplets during evaporation from surfaces were in situ investigated to further understand the stability of coatings against Wenzel transition. A droplet on a microporous coating gradually transformed to the Wenzel state and lost its spherical shape as the droplet volume decreased (i.e., the internal pressure of the droplet increased). The contact line of the droplet during evaporation remained almost unchanged. In contrast, a water droplet on a double-layer surface preserved its spherical shape even at the last stages of the evaporation process, where pressure differences as high as a few thousand pascals were generated. For this case, the droplet contact line retracted during evaporation and the droplet recovered the initial water contact angle. The demonstrated method for the preparation of robust transparent superhydrophobic coatings is promising for outdoor applications such as self-cleaning cover glasses for solar cells and nonwetting windows. KEYWORDS: Cassie state stability, superhydrophobic, self-cleaning, wettability, evaporation, organically modified silica ■ INTRODUCTIONA water droplet sitting on a superhydrophobic surface (i.e., the water contact angle is >150°) can be in either the Wenzel or Cassie state depending on the morphology and chemistry of the surface. In the Wenzel state, the surface is completely wetted and the droplet pins to the surface, whereas in the Cassie state, the droplet wets the surface partially and air pockets form between the surface and water droplet. 1−3 The Cassie state of wetting provides a large apparent water contact angle with low contact-angle hysteresis and results in a roll-off superhydrophobic surface, which is desired for practical applications such as self-cleaning windows and solar panels, 4−6 underwater drag reduction, 7,8 and anticorrosion coatings. 9 Various successful methods have been developed by mimicking well-known examples from nature (e.g., Lotus leaves and butterfly wings) to prepare artificial superhydrophobic surfaces with the Cassie state of wetting using lithographic methods, 10−12 sol−gel techniques, 4,9,13−15 phase separation in polymer blends, 16 electrospinning, 17,18 and others. 5,19−23 However, the Cassie state of ...

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Breaking the diffusion limit with super-hydrophobic delivery of molecules to plasmonic nanofocusing SERS structures

Cited by 666 publications

References 42 publications

Macroscale Plasmonic Substrates for Highly Sensitive Surface‐Enhanced Raman Scattering

Macroscale Plasmonic Substrates for Highly Sensitive Surface‐Enhanced Raman Scattering

Ultrasensitive surface-enhanced Raman scattering detection in common fluids

Robust Cassie State of Wetting in Transparent Superhydrophobic Coatings

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