In the present work, the standard monometallic localized surface plasmon resonance (LSPR) biosensing sensitivity is highly improved when using a new system based on glass substrates modified with high-temperature annealed gold/silver bimetallic nanoparticles (Au/Ag bimetallic NPs) coated with polydopamine films before biomolecule specific immobilization. Thus, different zones of bimetallic NPs are spatially created onto a glass support thanks to a commercial transmission electron microscopy (TEM) grid marker in combination with two sequential evaporations of continuous films of gold (4 nm) and silver (2 nm) and followed by annealing at 500 °C for 8 h. By using the scanning electron microscopy (SEM), it is found that annealed Au/Ag bimetallic NPs have uniform size and shape distribution that exhibited a sharper well-defined LSPR resonant peak when compared with that of monometallic Au NPs and thereby contributing to an improved sensitivity in LSPR biosensor application. The controlled micropatterns consisting of bimetallic particles are used in the construction of LSPR biochips for high-throughput detection of different concentrations of a model antigen named bovine serum albumin (BSA) on a single glass sample, with a lower limit of detection of 0.01 ng/mL under the optimized conditions.
A strong interest exists in developing
surface-enhanced Raman spectroscopy
(SERS) substrates that uniformly enhance Raman signals of chemical
and biological molecules over large scales while reaching the detection
limit of trace concentrations. Even though the resonant excitation
of localized surface plasmons of single or assembled metallic nanoparticles
used in SERS substrates can induce large electromagnetic fields, these
substrates display a SERS activity which suffers from poor reproducibility,
uniformity, and stability, preventing them from being reliable for
applications. In this work, we have developed self-supported large
scale Ag/Au bimetallic SERS-active substrate with a high density of
nanoparticles and uniform hot spots. The resultant substrates are
very stable under ambient conditions, providing unchanging Raman enhancement
signals even after one year of fabrication, due to the protective
Au shell on the bimetallic nanoparticles. The Ag/Au bimetallic substrate
exhibits remarkable SERS enhancement for nonresonant molecules, permitting
the detection of trace concentrations reaching 10–13 mol/L.
Light
interaction with metal nanostructures exposes exciting phenomena
such as strong amplification and localization of electromagnetic fields.
In surface-enhanced Raman spectroscopy (SERS), the strong signal amplification
is attributed to two fundamental mechanisms, electromagnetic and chemical
enhancement (EM and CM, respectively). While the EM mechanism is accepted
as the main responsible for signal amplification, a long-standing
controversy on the CM mechanism’s role still prevails. The
CM contribution can be evidenced when compared to the nonenhanced
(or bulk) Raman signal as a change in intensity ratios, peak shifts,
or appearance of new Raman modes. However, it is also possible to
induce similar spectral variations by changing the relative orientation
between the electric field and molecule or when a high electric field
gradient is achieved. Therefore, in this work, we show specific spectral
changes in SERS affected by the molecular orientation, while changes
in other modes can be attributed to chemical enhancement. On the basis
of our experimental and quantum chemical results for cobalt phthalocyanine,
we identify low-frequency Raman modes (LFMs) sensitive to charge-transfer
compared to high-frequency modes (HFMs) that are rather sensitive
to geometrical effects and temperature changes. These results provide
new evidence on the role of molecule excitation/polarization that
comes now as a more general and dominant effect than the chemical
enhancement mechanism so far attributed to charge-transfer processes.
These findings make it possible to engineer multifunctional Raman
molecular probes with selective sensitivity to the local environment
(HFMs) and charge-transfer processes (LFMs).
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The fluorescence of photosystem I (PSI) trimers in proximity to bimetallic plasmonic nanostructures have been explored by single-molecule spectroscopy (SMS) at cryogenic temperature (1.6 K). PSI serves as a model for biological multichromophore-coupled systems with high potential for biotechnological applications. Plasmonic nanostructures are fabricated by thermal annealing of thin metallic films. The fluorescence of PSI has been intensified due to the coupling with plasmonic nanostructures. Enhancement factors up to 22.9 and 5.1 are observed for individual PSI complexes coupled to Au/Au and Ag/Au samples, respectively. Additionally, a wavelength dependence of fluorescence enhancement is observed, which can be explained by the multichromophoric composition of PSI.
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