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1.
ACS Nano ; 14(2): 2542-2552, 2020 02 25.
Artigo em Inglês | MEDLINE | ID: mdl-32049493

RESUMO

Successful translation of laboratory-based surface-enhanced Raman scattering (SERS) platforms to clinical applications requires multiplex and ultratrace detection of small biomarker molecules from a complex biofluid. However, these biomarker molecules generally exhibit low Raman scattering cross sections and do not possess specific affinity to plasmonic nanoparticle surfaces, significantly increasing the challenge of detecting them at low concentrations. Herein, we demonstrate a "confine-and-capture" approach for multiplex detection of two families of urine metabolites correlated with miscarriage risks, 5ß-pregnane-3α,20α-diol-3α-glucuronide and tetrahydrocortisone. To enhance SERS signals by 1012-fold, we use specific nanoscale surface chemistry for targeted metabolite capture from a complex urine matrix prior to confining them on a superhydrophobic SERS platform. We then apply chemometrics, including principal component analysis and partial least-squares regression, to convert molecular fingerprint information into quantifiable readouts. The whole screening procedure requires only 30 min, including urine pretreatment, sample drying on the SERS platform, SERS measurements, and chemometric analyses. These readouts correlate well with the pregnancy outcomes in a case-control study of 40 patients presenting threatened miscarriage symptoms.

2.
ACS Nano ; 14(1): 28-117, 2020 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-31478375

RESUMO

The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.

3.
ACS Nano ; 13(10): 12090-12099, 2019 Oct 22.
Artigo em Inglês | MEDLINE | ID: mdl-31518107

RESUMO

Stand-off Raman spectroscopy combines the advantages of both Raman spectroscopy and remote detection to retrieve molecular vibrational fingerprints of chemicals at inaccessible sites. However, it is currently restricted to the detection of pure solids and liquids and not widely applicable for dispersed molecules in air. Herein, we realize real-time stand-off SERS spectroscopy for remote and multiplex detection of atmospheric airborne species by integrating a long-range optic system with a 3D analyte-sorbing metal-organic framework (MOF)-integrated SERS platform. Formed via the self-assembly of Ag@MOF core-shell nanoparticles, our 3D plasmonic architecture exhibits micrometer thick SERS hotspot to allow active sorption and rapid detection of aerosols, gas, and volatile organic compounds down to parts-per-billion levels, notably at a distance up to 10 m apart. The platform is highly sensitive to changes in atmospheric content, as demonstrated in the temporal monitoring of gaseous CO2 in several cycles. Importantly, we demonstrate the remote and multiplex quantification of polycyclic aromatic hydrocarbon mixtures in real time under outdoor daylight. By overcoming core challenges in current remote Raman spectroscopy, our strategy creates an opportunity in the long-distance and sensitive monitoring of air/gaseous environment at the molecular level, which is especially important in environmental conservation, disaster prevention, and homeland defense.

4.
Chem Soc Rev ; 48(3): 731-756, 2019 Feb 04.
Artigo em Inglês | MEDLINE | ID: mdl-30475351

RESUMO

Surface-enhanced Raman scattering (SERS) is a molecule-specific spectroscopic technique with diverse applications in (bio)chemistry, clinical diagnosis and toxin sensing. While hotspot engineering has expedited SERS development, it is still challenging to detect molecules with no specific affinity to plasmonic surfaces. With the aim of improving detection performances, we venture beyond hotspot engineering in this tutorial review and focus on emerging material design strategies to capture and confine analytes near SERS-active surfaces as well as various promising hybrid SERS platforms. We outline five major approaches to enhance SERS performance: (1) enlarging Raman scattering cross-sections of non-resonant molecules via chemical coupling reactions; (2) targeted chemical capturing of analytes through surface-grafted agents to localize them on plasmonic surfaces; (3) physically confining liquid analytes on non-wetting SERS-active surfaces and (4) confining gaseous analytes using porous materials over SERS hotspots; (5) synergizing conventional metal-based SERS platforms with functional materials such as graphene, semiconducting materials, and piezoelectric polymers. These approaches can be integrated with engineered hotspots as a multifaceted strategy to further boost SERS sensitivities that are unachievable using hotspot engineering alone. Finally, we highlight current challenges in this research area and suggest new research directions towards efficient SERS designs critical for real-world applications.

5.
Angew Chem Int Ed Engl ; 57(52): 17058-17062, 2018 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-30382604

RESUMO

Gas-liquid reactions form the basis of our everyday lives, yet they still suffer poor reaction efficiency and are difficult to monitor in situ, especially at ambient conditions. Now, an inert gas-liquid reaction between aniline and CO2 is driven at 1 atm and 298 K by selectively concentrating these immiscible reactants at the interface between metal-organic framework and solid nanoparticles (solid@MOF). Real-time reaction SERS monitoring and simulations affirm the formation of phenylcarbamic acid, which was previously undetectable because they are unstable for post-reaction treatments. The solid@MOF ensemble gives rise to a more than 28-fold improvement to reaction efficiency as compared to ZIF-only and solid-only platforms, emphasizing that the interfacial nanocavities in solid@MOF are the key to enhance the gas-liquid reaction. Our strategy can be integrated with other functional materials, thus opening up new opportunities for ambient-operated gas-liquid applications.

6.
Nanoscale ; 10(34): 16005-16012, 2018 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-30113061

RESUMO

Nanoporous gold (NPG) promises efficient light-to-heat transformation, yet suffers limited photothermal conversion efficiency owing to the difficulty in controlling its morphology for the direct modulation of thermo-plasmonic properties. Herein, we showcase a series of shape-controlled NPG nanoparticles with distinct bowl- (NPG-B), tube- (NPG-T) and plate-like (NPG-P) structures for quantitative temperature regulation up to 140 °C in <1 s using laser irradiation. Notably, NPG-B exhibits the highest photothermal efficiency of 68%, which is >12 and 39 percentage points better than those of other NPG shapes (NPG-T, 56%; NPG-P, 49%) and Au nanoparticles (29%), respectively. We attribute NPG-B's superior photothermal performance to its >13% enhanced light absorption cross-section compared to other Au nanostructures. We further realize an ultrasensitive heat-mediated light-to-mechanical "kill switch" by integrating NPG-B with a heat-responsive shape-memory polymer (SMP/NPG-B). This SMP/NPG-B hybrid is analogous to a photo-triggered mechanical arm, and can be activated swiftly in <4 s simply by remote laser irradiation. Achieving remotely-activated "kill switch" is critical in case of emergencies such as gas leaks, where physical access is usually prohibited or dangerous. Our work offers valuable insights into the structural design of NPG for optimal light-to-heat conversion, and creates opportunities to formulate next-generation smart materials for on-demand and multi-directional responsiveness.

7.
Nat Commun ; 9(1): 2769, 2018 07 17.
Artigo em Inglês | MEDLINE | ID: mdl-30018282

RESUMO

Organizing nanoparticles into supercrystals comprising multiple structures remains challenging. Here, we achieve one assembly with dual structures for Ag polyhedral building blocks, comprising truncated cubes, cuboctahedra, truncated octahedra, and octahedra. We create two micro-environments in a solvent evaporation-driven assembly system: one at the drying front and one at the air/water interface. Dynamic solvent flow concentrates the polyhedra at the drying front, generating hard particle behaviors and leading to morphology-dependent densest-packed bulk supercrystals. In addition, monolayers of nanoparticles adsorb at the air/liquid interface to minimize the air/liquid interfacial energy. Subsequent solvent evaporation gives rise to various structurally diverse dual-structure supercrystals. The topmost monolayers feature distinct open crystal structures with significantly lower packing densities than their densest-packed supercrystals. We further highlight a 3.3-fold synergistic enhancement of surface-enhanced Raman scattering efficiency arising from these dual-structure supercrystals as compared to a uniform one.

8.
Sci Adv ; 4(3): eaar3208, 2018 03.
Artigo em Inglês | MEDLINE | ID: mdl-29536047

RESUMO

Electrochemical nitrogen-to-ammonia fixation is emerging as a sustainable strategy to tackle the hydrogen- and energy-intensive operations by Haber-Bosch process for ammonia production. However, current electrochemical nitrogen reduction reaction (NRR) progress is impeded by overwhelming competition from the hydrogen evolution reaction (HER) across all traditional NRR catalysts and the requirement for elevated temperature/pressure. We achieve both excellent NRR selectivity (~90%) and a significant boost to Faradic efficiency by 10 percentage points even at ambient operations by coating a superhydrophobic metal-organic framework (MOF) layer over the NRR electrocatalyst. Our reticular chemistry approach exploits MOF's water-repelling and molecular-concentrating effects to overcome HER-imposed bottlenecks, uncovering the unprecedented electrochemical features of NRR critical for future theoretical studies. By favoring the originally unfavored NRR, we envisage our electrocatalytic design as a starting point for high-performance nitrogen-to-ammonia electroconversion directly from water vapor-abundant air to address increasing global demand of ammonia in (bio)chemical and energy industries.

9.
Angew Chem Int Ed Engl ; 57(20): 5792-5796, 2018 05 14.
Artigo em Inglês | MEDLINE | ID: mdl-29569823

RESUMO

Molecular-level airborne sensing is critical for early prevention of disasters, diseases, and terrorism. Currently, most 2D surface-enhanced Raman spectroscopy (SERS) substrates used for air sensing have only one functional surface and exhibit poor SERS-active depth. "Aerosolized plasmonic colloidosomes" (APCs) are introduced as airborne plasmonic hotspots for direct in-air SERS measurements. APCs function as a macroscale 3D and omnidirectional plasmonic cloud that receives laser irradiation and emits signals in all directions. Importantly, it brings about an effective plasmonic hotspot in a length scale of approximately 2.3 cm, which affords 100-fold higher tolerance to laser misalignment along the z-axis compared with 2D SERS substrates. APCs exhibit an extraordinary omnidirectional property and demonstrate consistent SERS performance that is independent of the laser and analyte introductory pathway. Furthermore, the first in-air SERS detection is demonstrated in stand-off conditions at a distance of 200 cm, highlighting the applicability of 3D omnidirectional plasmonic clouds for remote airborne sensing in threatening or inaccessible areas.

10.
Chem Commun (Camb) ; 54(20): 2546-2549, 2018 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-29464255

RESUMO

Timely detection of toxic vapor is vital for safeguarding people's lives. Herein, we design a plasmonic nose based on a zeolitic imidazolate framework (ZIF)-encapsulated Ag nanocube array for ultratrace recognition of VOC vapor. The plasmonic nose enables in situ adsorption kinetics and recognition of various VOCs at ppm levels, eliminating false positives. Our approach provides a paradigm shift to next-generation, effective and specific gas sensors.

11.
ACS Appl Mater Interfaces ; 9(45): 39584-39593, 2017 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-29020445

RESUMO

We demonstrate a one-step precise direct metal writing of well-defined and densely packed gold nanoparticle (AuNP) patterns with tunable physical and optical properties. We achieve this by using two-photon lithography on a Au precursor comprising poly(vinylpyrrolidone) (PVP) and ethylene glycol (EG), where EG promotes higher reduction rates of Au(III) salt via polyol reduction. Hence, clusters of monodisperse AuNP are generated along raster scanning of the laser, forming high-particle-density, well-defined structures. By varying the PVP concentration, we tune the AuNP size from 27.3 to 65.0 nm and the density from 172 to 965 particles/µm2, corresponding to a surface roughness of 12.9 to 67.1 nm, which is important for surface-based applications such as surface-enhanced Raman scattering (SERS). We find that the microstructures exhibit an SERS enhancement factor of >105 and demonstrate remote writing of well-defined Au microstructures within a microfluidic channel for the SERS detection of gaseous molecules. We showcase in situ SERS monitoring of gaseous 4-methylbenzenethiol and real-time detection of multiple small gaseous species with no specific affinity to Au. This one-step, laser-induced fabrication of AuNP microstructures ignites a plethora of possibilities to position desired patterns directly onto or within most surfaces for the future creation of multifunctional lab-on-a-chip devices.

12.
ACS Appl Mater Interfaces ; 9(45): 39635-39640, 2017 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-29048876

RESUMO

Miniaturizing the continuous multistep operations of a factory into a microchemical plant offers a safe and cost-effective approach to promote high-throughput screening in drug development and enforcement of industrial/environmental safety. While particle-assembled microdroplets in the form of liquid marble are ideal as microchemical plant, these platforms are mainly restricted to single-step reactions and limited to ex situ reaction monitoring. Herein, we utilize plasmonic liquid marble (PLM), formed by encapsulating liquid droplet with Ag nanocubes, to address these issues and demonstrate it as an ideal microchemical plant to conduct reaction-and-detection sequences on-demand in a nondisruptive manner. Utilizing a two-step azo-dye formation as our model reaction, our microchemical plant allows rapid and efficient diazotization of nitroaniline to form diazonium nitrobenzene, followed by the azo coupling of this intermediate with target aromatic compound to yield azo-dye. These molecular events are tracked in situ via SERS measurement through the plasmonic shell and further verified with in silico investigation. Furthermore, we apply our microchemical plant for ultrasensitive SERS detection and quantification of bisphenol A (BPA) with detection limit down to 10 amol, which is 50 000-fold lower than the BPA safety limit. Together with the protections offered by plasmonic shell against external environments, these collective advantages empower PLM as a multifunctional microchemical plant to facilitate small-volume testing and optimization of processes relevant in industrial and research contexts.

13.
J Am Chem Soc ; 139(33): 11513-11518, 2017 08 23.
Artigo em Inglês | MEDLINE | ID: mdl-28743183

RESUMO

We demonstrate a molecular-level observation of driving CO2 molecules into a quasi-condensed phase on the solid surface of metal nanoparticles (NP) under ambient conditions of 1 bar and 298 K. This is achieved via a CO2 accumulation in the interface between a metal-organic framework (MOF) and a metal NP surface formed by coating NPs with a MOF. Using real-time surface-enhanced Raman scattering spectroscopy, a >18-fold enhancement of surface coverage of CO2 is observed at the interface. The high surface concentration leads CO2 molecules to be in close proximity with the probe molecules on the metal surface (4-methylbenzenethiol), and transforms CO2 molecules into a bent conformation without the formation of chemical bonds. Such linear-to-bent transition of CO2 is unprecedented at ambient conditions in the absence of chemical bond formation, and is commonly observed only in pressurized systems (>105 bar). The molecular-level observation of a quasi-condensed phase induced by MOF coating could impact the future design of hybrid materials in diverse applications, including catalytic CO2 conversion and ambient solid-gas operation.

14.
Angew Chem Int Ed Engl ; 56(30): 8813-8817, 2017 07 17.
Artigo em Inglês | MEDLINE | ID: mdl-28544200

RESUMO

Liquid marbles are emergent microreactors owing to their isolated environment and the flexibility of materials used. Plasmonic liquid marbles (PLMs) are demonstrated as the smallest spectroelectrochemical microliter-scale reactor for concurrent spectro- and electrochemical analyses. The three-dimensional Ag shell of PLMs are exploited as a bifunctional surface-enhanced Raman scattering (SERS) platform and working electrode for redox process modulation. The combination of SERS and electrochemistry (EC) capabilities enables in situ molecular read-out of transient electrochemical species, and elucidate the potential-dependent and multi-step reaction dynamics. The 3D configuration of our PLM-based EC-SERS system exhibits 2-fold and 10-fold superior electrochemical and SERS performance than conventional 2D platforms. The rich molecular-level electrochemical insights and excellent EC-SERS capabilities offered by our 3D spectroelectrochemical system are pertinent in charge transfer processes.

15.
Angew Chem Int Ed Engl ; 56(20): 5565-5569, 2017 05 08.
Artigo em Inglês | MEDLINE | ID: mdl-28398608

RESUMO

3D plasmonic colloidosomes are superior SERS sensors owing to their high sensitivity and excellent tolerance to laser misalignment. Herein, we incorporate plasmonic colloidosomes in a microfluidic channel for online SERS detection. Our method resolves the poor signal reproducibility and inter-sample contamination in the existing online SERS platforms. Our flow system offers rapid and continuous online detection of 20 samples in less than 5 min with excellent signal reproducibility. The isolated colloidosomes prevent cross-sample and channel contamination, allowing accurate quantification of samples over a concentration range of five orders of magnitude. Our system demonstrates high-resolution multiplex detection with fully preserved signal and Raman features of individual analytes in a mixture. High-throughput multi-assay analysis is performed, which highlights that our system is capable of rapid identification and quantification of a sequence of samples containing various analytes and concentrations.

16.
J Phys Chem Lett ; 8(1): 243-249, 2017 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-27977926

RESUMO

The ability of an artificial microdroplet to mimic the rotational behaviors of living systems is crucial for dynamic mass transportation but remains challenging to date. Herein, we report dynamic microdroplet rotation using a liquid marble (RLM) and achieve precise control over mass transportation and distribution in a three-dimensional (3D) microdroplet. RLM rotates synchronously with an external magnetic field, creating circular hydrodynamic flow and an outward centrifugal force. Such spin-induced phenomena direct a spiral movement of entrapped molecules and accelerate their diffusion and homogenization in the entire liquid. Moreover, we demonstrate the rotation rate-controlled (between 0 and 1300 rpm) modulation of shell-catalyzed reaction kinetics from 0.13 to 0.62 min-1. The directed acceleration of reactants toward a catalytically active shell surface is 3-fold faster than conventional stir bar-based convective flow. RLM as an efficient magnetohydrodynamics transducer will be valuable for dynamical control over mass transportation in microdroplet-based chemical, biological, and biomedical studies.

17.
ACS Appl Mater Interfaces ; 8(36): 23941-6, 2016 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-27548629

RESUMO

Liquid marble offers an attractive droplet manipulation approach by isolating microdroplet in a nonstick encapsulating shell formed via the spontaneous coating of hydrophobic particles onto the liquid surface. While liquid marble prepared using magnetic nanoparticles enables precise spatiotemporal actuation of microdroplets, these manipulations are generally limited to simple and linear spatial maneuver of microdroplets. Herein, we demonstrate the unique and three-dimensional spinning of microliter-sized liquid marble (LM) and its subsequent dual applications as (1) the world's smallest centrifuge and (2) a miniature and localized viscometer. Our LM is responsive to an applied rotating magnetic field, with its spinning speed programmable between 0 and 1300 rpm. This spinning generates an unprecedented centrifugal force of >2g in a LM of ∼1 mm radius. Such centrifugal force facilitates an outward and radial hydrodynamic flow in the enclosed microdroplet, enabling LM to serve as a microcentrifuge for the sedimentation of nanoparticles with >85% separation efficiency. Furthermore, we apply spinning LM as an ultrasensitive spin-to-viscosity transducer to quantify the viscosity of the external suspended liquid in the relative viscosity (η/ηwater) range of 1-70 using ≤1 mL liquid sample. Collectively, the ensemble of benefits offered by spinning LM creates enormous opportunities in the development of multifunctional micromagneto-mechanical devices as promising surface-sensitive microsensor, miniature centrifugal pump, and even microreactor with directed heat and mass transfer mechanism.

18.
Small ; 12(33): 4531-40, 2016 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-27389580

RESUMO

Controlling sub-10 nm ligament sizes and open-shell structure in nanoporous gold (NPG) to achieve strained lattice is critical in enhancing catalytic activity, but it remains a challenge due to poor control of reaction kinetics in conventional dealloying approach. Herein, a ligament size-controlled synthesis of open-shell NPG bowls (NPGB) through hetero-epitaxial growth of NPGB on AgCl is reported. The ligament size in NPGB is controlled from 6 to 46 nm by varying the hydroquinone to HAuCl4 ratio. The Williamson-Hall analysis demonstrates a higher lattice strain in smaller ligament size. In particular, NPGB with 6 nm (NPGB 6) ligament size possess the highest strain of 15.4 × 10(-3) , which is nearly twice of conventional 2D NPG sheets (≈8.8 × 10(-3) ). The presence of high surface energy facets in NPGBs is also envisaged. The best electrocatalytic activity toward methanol oxidation is observed in NPGB 6 (27.8 µA µg(-1) ), which is ≈9-fold and 3-fold higher than 8 nm solid Au nanoparticles, and conventional NPG sheets. The excellent catalytic activity in NPGB 6 is attributed to the open-shell structure, lattice strain, and higher electro-active surface area, allowing efficient exposure of catalytic active sites to facilitate the methanol oxidation. The results offer a potential strategy for designing next generation electrocatalysts.

19.
Analyst ; 141(17): 5107-12, 2016 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-27405973

RESUMO

Current substrate-less SERS platforms are limited to uncontrolled aggregation of plasmonic nanoparticles or quasi-crystalline arrays of spherical nanoparticles, with no study on how the lattice structures formed by nanoparticle self-assembly affect their detection capabilities. Here, we organize Ag octahedral building blocks into two large-area plasmonic metacrystals at the oil/water interface, and investigate their in situ SERS sensing capabilities. Amphiphilic octahedra assemble into a hexagonal close-packed metacrystal, while hydrophobic octahedra assemble into an open square metacrystal. The lower packing density square metacrystal gives rise to much stronger SERS enhancement than the denser packing hexagonal metacrystal, arising from the larger areas of plasmonic hotspots within the square metacrystal at the excitation wavelength. We further demonstrate the ability of the square metacrystal to achieve quantitative ultratrace detection of analytes from both the aqueous and organic phases. Detection limits are at the nano-molar levels, with analytical enhancement factors reaching 10(8). In addition, multiplex detection across both phases can be achieved in situ without any loss of signal quantitation.

20.
Angew Chem Int Ed Engl ; 55(29): 8304-8, 2016 07 11.
Artigo em Inglês | MEDLINE | ID: mdl-27239973

RESUMO

Miniaturized liquid-liquid interfacial reactors offer enhanced surface area and rapid confinement of compounds of opposite solubility, yet they are unable to provide in situ reaction monitoring at a molecular level at the interface. A picoreactor operative at the liquid-liquid interface is described, comprising plasmonic colloidosomes containing Ag octahedra strategically assembled at the water-in-decane emulsion interface. The plasmonic colloidosomes isolate ultrasmall amounts of solutions (<200 pL), allowing parallel monitoring of multiple reactions simultaneously. Using the surface-enhanced Raman spectroscopy (SERS) technique, in situ monitoring of the interfacial protonation of dimethyl yellow (p-dimethylaminoazobenzene (DY)) is performed, revealing an apparent rate constant of 0.09 min(-1) for the first-order reaction. The presence of isomeric products with similar physical properties is resolved, which would otherwise be indiscernible by other analytical methods.

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