“Superchiral” Spectroscopy: Detection of Protein Higher Order Hierarchical Structure with Chiral Plasmonic Nanostructures

Tullius, Ryan; Karimullah, Affar S.; Rodier, Marion; Fitzpatrick, Brian; Gadegaard, Nikolaj; Barron, Laurence D.; Rotello, Vincent M.; Cooke, Graeme; Lapthorn, A.J.; Kadodwala, Malcolm

doi:10.1021/jacs.5b04806

Cited by 192 publications

(242 citation statements)

References 28 publications

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“…[115] In most cases, chiral biomolecules detection has been achieved by measuring the EM fields via manipulating plas monic structures. [116,117] It has increased the sensitivity of effec tive refractive index measuring. Ultrasensitive detection of bio molecules with superchiral EM fields has been achieved.…”

Section: Detecting and Sensingmentioning

confidence: 99%

Plasmonic Chiral Nanostructures: Chiroptical Effects and Applications

Luo

Chi

Jiang

et al. 2017

Advanced Optical Materials

170

122

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(circular birefringence) and absorption losses (circular dichroism) with the circu larly polarized light (CPL) illumination. [10] CB arises from the difference in the real part of refractive index, leading to a dif ferent velocity for LCP and RCP compo nents, and thus results in the polarization rotation of the linearly polarized incident light. CD corresponds to the difference in the imaginary part of refractive index, resulting in a distinct absorption loss for LCP and RCP excitations. Besides the con ventional CD and CB, asymmetric trans mission (circular conversion dichroism) is another fundamental chiroptical pheno menon, which exists in the nondiffracting array, referring to different LCPtoRCP and RCPtoLCP conversion efficiencies. [11] All of these chiroptical phenomena have been successfully applied in the spectros copy for identifying special arrangements of chiral matters in biology, chemistry and physics as efficient diagnostic tools. [12][13][14][15][16] However, the chirop tical response in natural chiral materials is relatively weak due to the small electromagnetic (EM) interaction volume, [17] hence limits its further applications.Recent progress in plasmonics paves the way for the enhancement of chiroptical response. [18][19][20] Surface plasmons (SPs), as the collective electrons oscillation at the dielectric and metal interface, [21][22][23] present the capacity of light confine ment and field enhancement, which significantly improve the strength of lightmatter interactions. [24][25][26][27][28] With the uptodate nanofabrication technology, the study field of chirality has been extended from traditional chiral molecules to 3D metallic nanostructures. [29][30][31][32] Chiroptical responses of metallic meta molecules have been widely investigated, [33][34][35] and applied in various fields, such as biosensing, [36] chiral catalysis, [37] polari zation tuning, [38] and chiral photo detection.[39] The 3D metallic structure exhibited giant optical activity response because of the strong interaction between electric and magnetic resonant modes. [40,41] Different from 3D chiral ensembles, planar chiral structures show none chiral effect, as they can always coincide with their mirror images. However, 2D chirality was successfully found in the quasitwodimensional (quasi2D) chiral structure. [42] Moreover, recent reports show that even achiral nanomaterials have the ability to generate strong CD under an oblique CPL illumination. [43] This kind of extrinsic chirality arises from sym metry breaking of the incident light and the quasi2D material, which is quite different from the intrinsic chirality of 3D chiral The plasmonic chiroptical effect has been used to manipulate chiral states of light, where the strong field enhancement and light localization in metallic nanostructures can amplify the chiroptical response. Moreover, in metamaterials, the chiroptical effect leads to circular dichroism (CD), circular birefringence (CB), and asymmetric transmission. Potential applications enabled by chiral plasmonics...

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Section: Detecting and Sensingmentioning

confidence: 99%

Plasmonic Chiral Nanostructures: Chiroptical Effects and Applications

Luo

Chi

Jiang

et al. 2017

Advanced Optical Materials

170

122

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“…[25][26][27][28][29] In particular, these chiral assemblies can be used to enhance the dissymmetric factor of chiral molecules either through exciting superchiral electromagnetic fields near the plasmonic inclusions or via strong near-field interaction between chiral molecules and plasmonic elements. [33][34][35] Although these bottom-up methods can produce chiral metamolecules in large amount and at low cost, the chiral performance and structure reproducibility of the samples made with these methods often are not comparable to that fabricated by the aforementioned top-down techniques. [33][34][35] Although these bottom-up methods can produce chiral metamolecules in large amount and at low cost, the chiral performance and structure reproducibility of the samples made with these methods often are not comparable to that fabricated by the aforementioned top-down techniques.…”

mentioning

confidence: 99%

Ultrabroadband Optical Superchirality in a 3D Stacked‐Patch Plasmonic Metamaterial Designed by Two‐Step Glancing Angle Deposition

Hou

Leung

Chan

et al. 2016

Adv Funct Materials

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7807wileyonlinelibrary.com respectively from the interaction of circularly or linearly polarized light with structurally chiral media in nature, such as chiral (bio)molecules and solids without any mirror symmetry. From the viewpoint of classical electrodynamics, the degeneracy between the helicity eigenmodes of light, i.e., left and right circularly polarized (LCP and RCP) waves, is broken due to cross coupling between the electric and magnetic dipoles in a chiral medium, leading to differential extinction (CD) or transmission (optical activity) for LCP/ RCP waves. These chiroptical effects provide an effective approach for manipulating polarization states of light in various optical and photonic applications, and also for sensing enantiomers of chemical molecules and determining structural conformation of biological molecules. However, these effects induced by magnetoelectric coupling in natural materials, particularly in biomolecules like amino acids, sugars, proteins, and viruses, are often very weak. [1] This unfavorable feature not only limits the ability of naturally occurring materials to effectively manipulate light polarization at the nanoscale, particularly for nanophotonics applications, but also severely restricts the application of chirality-sensitive spectroscopic techniques to samples at the microgram level. [1][2][3] Recently, plasmonic chiral metamaterials (PCMs) made of subwavelength metal nanostructures, artificially engineered chiral resonators that cannot be superimposed on their mirror images, have attracted a considerable amount of research interest. Compared with naturally occurring materials, they often have significantly enhanced chirality and thus enable many fascinating phenomena such as pronounced linear [4][5][6][7] and nonlinear chiroptical effects, [8,9] negative refraction, [10][11][12] manipulating Casimir effect, [13][14][15] unusual spin Hall effect of light, [16] and chiral-selective nonlinear imaging. [17,18] Depending on their spatial dimensions, the PCMs developed thus far can be either 2D (or planar) or 3D. The planar 2D PCMs are composed of periodic arrays of plasmonic resonators such as gold gammadions, [5,7] fish-scale, [19][20][21] and G-shape nanostructures, [22] and their chiroptical effects are generally asymmetric with respect Low-cost and large-scale fabrication of 3D chiral metamaterials is highly desired for potential applications such as nanophotonics devices and chiral biosensors. One of the promising fabrication methods is to use glancing angle deposition (GLAD) of metal on self-assembled dielectric microsphere array. However, structural handedness varies locally due to long-range disorder of the array and therefore large-scale realization of the same handedness is impossible. Here, using symmetry considerations a two-step GLAD process is proposed to eliminate this longstanding problem. In the proposed scheme, the unavoidable long-range disorder gives rise to microscale domains of the same handedness but of slightly different structural geometries and ultima...

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“…1,5 Molecular CD of natural compounds such as organic and biological chiral molecules is typically very weak and occurs in the UV region (150-300 nm). [10][11][12][13][14][15][16] The major impediments lie in the fact that accurate positioning of a single chiral molecule in the vicinity of a plasmonic nanoparticle is a nontrival issue. Recently, theoretical calculations have predicted an induction of CD at the resonance of an achiral plasmonic nanoparticle, when it is placed in close proximity of a chiral molecule.…”

mentioning

confidence: 99%

“…Probing CD signatures of chiral molecules beyond the UV region with large magnitudes is thus of great interest. To date, only a limited number of experimental works has demonstrated the existence of plasmon-induced CD by using a large number of chiral molecules, which are attached on metal nanoparticles [10][11][12] or on planar plasmonic nanostructure chips [13][14][15][16] . [6][7][8][9] This plasmon-induced CD can manifest itself as distinct spectral features in the visible range, which are far from the CD band of the chiral molecule.…”

mentioning

confidence: 99%

Understanding complex chiral plasmonics

2015

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Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the 'host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant and simple analytical model, which can describe, predict, and comprehend the chiroptical spectra in detail. Our study will shed light on designing well-controlled chiral-achiral coupling platforms for reliable chiral sensing.

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“Superchiral” Spectroscopy: Detection of Protein Higher Order Hierarchical Structure with Chiral Plasmonic Nanostructures

Cited by 192 publications

References 28 publications

Plasmonic Chiral Nanostructures: Chiroptical Effects and Applications

Plasmonic Chiral Nanostructures: Chiroptical Effects and Applications

Ultrabroadband Optical Superchirality in a 3D Stacked‐Patch Plasmonic Metamaterial Designed by Two‐Step Glancing Angle Deposition

Understanding complex chiral plasmonics

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