Abstract:Detection of enantiomers is a challenging problem in drug development as well as environmental and food quality monitoring where traditional optical detection methods suffer from low signals and sensitivity. Application...
“…For the point C located exactly on the symmetry axis, the total decay rate and radiative decay rate of the RCP and LCP emitters are almost equal (Figure h). Note also that plasmonic nanostructures and metasurfaces with intrinsic structural chirality have been reported to achieve chiral-dependent emission behaviors such as chiral photoluminescence and surface-enhanced Raman scattering–chiral anisotropy, as well as an enantiomer-dependent tailored immunological response. − ,, Here, it is shown that chiral-dependent QE exists even in the symmetric antenna, which lacks the chiral near-field and structural chirality. In addition to previous studies on chiral sensing, − chiral QE can provide an additional perspective for detecting enantiomers to optimize the sensitivity of chiral identification.…”
Section: Resultsmentioning
confidence: 81%
“…The superscript ± indicates the right/left circularly polarized (RCP/LCP) emitter. Assuming that the collection efficiency remains constant when the chiral emitter is coupled to the nanostructure, the chiral detection sensitivity can be enhanced by nanostructures that generate near-field with increased local field intensity or chiral asymmetry. − For instance, recent studies have achieved chiral-sensitive enantiomeric discrimination in surface-enhanced Raman scattering response or luminescence from fluorescent species. − However, most previous works focused on the excitation enhancement during chiral sensing by engineering nanostructures to feature enhanced near-field optical chirality (OC). − To further understand the impact of the chiral near-field upon the emission process of molecules, we focus on the chiral response of luminescence QE in plasmonic nanostructures. Furthermore, the QE in TMDCs plasmonic hybrid differs for valley excitons with different spins. , Thus, chiral-dependent QE may improve the sensitivity of enantiomers’ chiral recognition.…”
Chiral detection is critical for investigating many biological processes. We use numerical calculations to study the quantum efficiency (QE) of a chiral emitter modulated by plasmonic antennas. The chiral difference in QE is discovered when the chiral emitter is placed in the vicinity of the antenna. The chiral QE is position-dependent for symmetric and asymmetric antennas and can be modulated by designing chiral configurations. The local optical chirality and the coupled harmonic oscillator model can qualitatively explain the QE difference revealed by the numerical methods. That originates from the interference between resonant modes with different phases induced by chiral interactions, resulting in the different loss of coupled modes. Our results provide extended design ideas for enantioselective fluorescent recognition of chiral molecules.
“…For the point C located exactly on the symmetry axis, the total decay rate and radiative decay rate of the RCP and LCP emitters are almost equal (Figure h). Note also that plasmonic nanostructures and metasurfaces with intrinsic structural chirality have been reported to achieve chiral-dependent emission behaviors such as chiral photoluminescence and surface-enhanced Raman scattering–chiral anisotropy, as well as an enantiomer-dependent tailored immunological response. − ,, Here, it is shown that chiral-dependent QE exists even in the symmetric antenna, which lacks the chiral near-field and structural chirality. In addition to previous studies on chiral sensing, − chiral QE can provide an additional perspective for detecting enantiomers to optimize the sensitivity of chiral identification.…”
Section: Resultsmentioning
confidence: 81%
“…The superscript ± indicates the right/left circularly polarized (RCP/LCP) emitter. Assuming that the collection efficiency remains constant when the chiral emitter is coupled to the nanostructure, the chiral detection sensitivity can be enhanced by nanostructures that generate near-field with increased local field intensity or chiral asymmetry. − For instance, recent studies have achieved chiral-sensitive enantiomeric discrimination in surface-enhanced Raman scattering response or luminescence from fluorescent species. − However, most previous works focused on the excitation enhancement during chiral sensing by engineering nanostructures to feature enhanced near-field optical chirality (OC). − To further understand the impact of the chiral near-field upon the emission process of molecules, we focus on the chiral response of luminescence QE in plasmonic nanostructures. Furthermore, the QE in TMDCs plasmonic hybrid differs for valley excitons with different spins. , Thus, chiral-dependent QE may improve the sensitivity of enantiomers’ chiral recognition.…”
Chiral detection is critical for investigating many biological processes. We use numerical calculations to study the quantum efficiency (QE) of a chiral emitter modulated by plasmonic antennas. The chiral difference in QE is discovered when the chiral emitter is placed in the vicinity of the antenna. The chiral QE is position-dependent for symmetric and asymmetric antennas and can be modulated by designing chiral configurations. The local optical chirality and the coupled harmonic oscillator model can qualitatively explain the QE difference revealed by the numerical methods. That originates from the interference between resonant modes with different phases induced by chiral interactions, resulting in the different loss of coupled modes. Our results provide extended design ideas for enantioselective fluorescent recognition of chiral molecules.
“…Therefore, measurement of L-Cys, TP, and its derivatives levels is important for clinical diagnosis and environmental restoration. Many optical as well as nonoptical analytical techniques have been used so far to detect thiols, such as chemiluminescence, voltammetry, fluorescence, photoelectrochemical methods, time-resolved photoluminescence spectroscopy, high-performance liquid chromatography (HPLC), electrochemical methods, and a handful of surface-enhanced Raman spectroscopy (SERS)-based methods. − However, most of these techniques suffer from individual drawbacks such as interference from other analytes, time-consuming operation, complex substrate preparation, and difficult synthesis of fluorescent probes. Additionally, the choice of analytical method to quantify the small molecule L-Cys and TPs should be based on the lowest limit of quantification (LOQ) because the lowest LOQ would allow for detection and quantification in the smallest amount of analytical sample, minimizing the volume of the sample collection.…”
Trimetallic Ag−Au−Cu alloy microflowers (MFs) with various surface compositions were synthesized on a glass coverslip and used as efficient surface-enhanced Raman spectroscopy (SERS) substrates for highly sensitive label-free detection of smaller Raman scattering crosssection molecules, namely, L-cysteine and toxic thiophenols. MFs of different compositions were synthesized via appropriate mixing of metal− alkyl ammonium halide precursors followed by a single-step thermolysis at 350 °C. While the Ag percentage was kept constant at 90% for all the substrates, the composition of Au and Cu was varied between 1 and 9% sequentially. The synthesized MFs were thoroughly characterized by using field emission scanning electron microscopy (FE-SEM), wide-angle X-ray scattering, X-ray photoelectron spectroscopy (XPS), and X-ray fluorescence techniques. FE-SEM studies revealed that the MFs were present throughout the substrate, and the average size varied from 20 to 40 μm. XPS studies showed that the top surface of the alloy substrates was rich in either Au or Cu atoms, while Ag remained underneath. The performance of the trimetallic MFs as SERS substrates was evaluated using Rhodamine 6G as a probe molecule, which showed that the MFs with Ag−Au−Cu compositions 90−7−3 and 90−3−7 were found to be the best and of equal SERS efficiency. The SERS enhancement factor (EF) of both these MFs was found to be the same, approximately 9 × 10 7 , when calculated using 1,2,3benzatriazole as the probe molecule. Between the two, the trimetallic substrate with a higher Au percentage (Ag−Au−Cu as 90−7− 3) was used for the sensitive SERS-based detection of thiols to exploit the strong Au−S binding interaction. By virtue of the high EF of the substrate, the inherently low Raman scattering cross-sections of the probe molecules were greatly enhanced in SERS mode. The 'limit of quantification (LOQ)' values were found to be 1 nM for aliphatic L-Cysteine and 1−0.1 pM for aromatic thiols using the trimetallic SERS sensor.
“…Despite the similar SERS signals obtained on D-Au-HO and D-Au-HDO, D-Au-HO exhibits a higher chiral discrimination ability than D-Au-HDO, indicating the enantioselective interaction of chiral electromagnetic fields and chiral molecules. This effect is also confirmed by excitation wavelength-dependent experiments and widely supported by previous literature. ,, We conducted experiments on different excitation wavelengths. Illuminating the D-Au-HO with 540 nm light achieves a higher value of chiral discriminating ability than illuminating with 620 nm light, owing to the high chiroptical response around 540 nm (Figure S21a,c), despite the similar plasmon-enhanced currents in both cases (Figures S14 and S21b).…”
mentioning
confidence: 99%
“…This effect is also confirmed by excitation wavelength-dependent experiments and widely supported by previous literature. 31,34,52 We conducted experiments on different excitation wavelengths. Illuminating the D-Au-HO with 540 nm light achieves a higher value of chiral discriminating ability than illuminating with 620 nm light, owing to the high chiroptical response around 540 nm (Figure S21a,c), despite the similar plasmon-enhanced currents in both cases (Figures S14 and S21b).…”
Surface roughness in chiral plasmonic
nanostructures generates
asymmetrical localized electromagnetic fields, which hold great promise
for applications in chiral recognition, chiroptical spectroscopic
sensing, and enantioselective photocatalysis. In this study, we develop
a surface topographical engineering approach to precisely manipulate
the surface structures of chiral Au nanocrystals. Through carefully
controlling the amounts of l- or d-cystine (Cys)
and the seed solution in the growth process, we successfully synthesize
chiral Au nanocrystals with highly disordered, ordered, and less ordered
wrinkled surfaces. An underlying principle governing the relationship
between surface roughness, orderliness, and chiroptical response is
also proposed. More importantly, the chiral ordered wrinkles on the
surfaces of the nanocrystals generate asymmetrical localized electronic
fields with enhanced intensity, which achieve excellent plasmon-enhanced
chiral discrimination ability for penicillamine (Pen) enantiomers.
This work offers exciting prospects for manipulating the surface structures
of chiral nanocrystals and designing highly sensitive plasmon-enhanced
enantioselective sensors with chiral hot spots.
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