SANS study of mixed cholesteric cellulose nanocrystal – gold nanorod suspensions

Rie, Jonas Van; González‐Rubio, Guillermo; Kumar, Sugam; Schütz, Christina; Kohlbrecher, J.; Vanroelen, Michèle; Gerven, Tom Van; Deschaume, Olivier; Bartic, Carmen; Liz‐Marzán, Luis M.; Salazar-Alvarez, Germán; Thielemans, Wim

doi:10.1039/d0cc04845c

Cited by 14 publications

(13 citation statements)

References 26 publications

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“…These SPR-determined effects can be tuned by adjusting the aspect ratio of the GNRs or the shape and composition of the plasmonic nanoparticles to match with desired excitation wavelengths, [25,26] which may facilitate imaging amyloid aggregates in situ in the near-IR range. Despite the similarities between our system and other hybrid liquid crystal colloids such as cellulose nanocrystals (CNCs) and GNRs, [23,29] the key difference observed here is the tactoids with concentrated doping nanoparticles. In the previously reported CNC-GNR codispersions, GNRs tend to be more concentrated in the isotropic region of the biphasic colloidal suspension.…”

Section: Resultsmentioning

confidence: 94%

“…Despite the similarities between our system and other hybrid liquid crystal colloids such as cellulose nanocrystals (CNCs) and GNRs, [ 23,29 ] the key difference observed here is the tactoids with concentrated doping nanoparticles. In the previously reported CNC‐GNR codispersions, GNRs tend to be more concentrated in the isotropic region of the biphasic colloidal suspension.…”

Section: Resultsmentioning

confidence: 97%

“…In the previously reported CNC-GNR codispersions, GNRs tend to be more concentrated in the isotropic region of the biphasic colloidal suspension. [23,29] Theoretical studies on binary mixtures of rod-like particles with different lengths also point out that longer rods tend to have higher concentrations in the anisotropic phase, while shorter ones have higher concentrations in the isotropic phase. [30,31] Therefore, it is unexpected and unconventional that in this system the GNRs, being much shorter than the fibrils, have a higher number density within the tactoids compared to that outside in the isotropic phase.…”

Section: Resultsmentioning

confidence: 99%

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Plasmonic Amyloid Tactoids

et al. 2021

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The potential of amyloid fibrils in artificial materials can be further enriched by their ability to form anisotropic assemblies. Like many other rod-like colloidal particles, aqueous suspensions of amyloid fibrils can self-assemble into phases with long-range orientational ordering, i.e., liquid crystals (LCs), driven by entropy. [11][12][13][14] In addition to the common nematic phase where there is no positional ordering, the inherent chirality of the fibrils also leads to cholesteric phases with helical twisting alignment of fibrils by controlling the fibrils length distribution and confinement. [15,16] These ordered states lead to anisotropy in the mechanical, rheological, and optical properties of the fibrils assemblies in meso-and macroscale, which, however, has yet to be taken full advantage of in the fabrication of functional materials. [7,8] An emerging research interest is the photonic properties of amyloid fibrils. First observed as UV-induced blue-green luminescence, [17] it has been extended to UV-vis-NIR range [18] and wavelength-dependent nonlinear absorption is also discovered in AFs. [19] Although the exact origin of the intrinsic fluorescence is still under debate, studies have demonstrated that it can be used to monitor the growth of the fibrils [20] or to image amyloid deposits in a noninvasive and contrast-agent-free fashion. [18,21] These findings may contribute to the diagnosis and treatment of human amyloidosis, as well as the development of novel bionanomaterials. However, the intrinsic fluorescence suffers from low quantum efficiency and weak signal to noise ratio, and therefore, hinders its potentials in practical applications. [18][19][20][21][22] In this work, we study the intrinsic fluorescence of amyloid fibrils in orientationally ordered phases and investigate their interaction with plasmonic nanoinclusions codispersed with the fibrils. We show that the fluorescence from the fibrils is dependent on the polarization of the excitation when they are in microdroplets with liquid crystalline ordering, i.e., tactoids. Then gold nanorods (GNRs) are introduced to the colloidal suspensions of AFs, forming hybrid tactoids with GNRs aligned by the LC orientation field of the fibrils. This alignment manifests through the selective activation of surface plasmon resonance (SPR) absorption bands of GNRs, resulting in color changes when illuminated with polarized white light. Furthermore, enhanced fluorescence from the hybrid material is observed due to the coupling between the GNRs' plasmonic effect and the fibrils' intrinsic fluorescence. The enhanced fluorescence is strongly dependent on the wavelength and polarization of the incident light, which is confirmed by numerical simulations of the electromagnetic field distribution in the vicinity of GNRs. We point out the unusual higher Despite their link to neurodegenerative diseases, amyloids of natural and synthetic sources can also serve as building blocks for functional materials, while possessing intrinsic photonic properties. Here, it is dem...

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

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Plasmonic Amyloid Tactoids

et al. 2021

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“…For water-based systems, the SANS is typically performed in D 2 O, because deuterium scatters more than hydrogen. Recently, van Rie et al . utilized SANS to investigate the alignment of gold nanorods in a chiral CNC suspension.…”

Section: Analysis Of Cncsmentioning

confidence: 99%

Cellulose Nanocrystal Liquid Crystal Phases: Progress and Challenges in Characterization Using Rheology Coupled to Optics, Scattering, and Spectroscopy

2021

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Cellulose nanocrystals (CNCs) self-assemble and can be flow-assembled to liquid crystalline orders in a water suspension. The orders range from nano- to macroscale with the contributions of individual crystals, their micron clusters, and macroscopic assemblies. The resulting hierarchies are optically active materials that exhibit iridescence, reflectance, and light transmission. Although these assemblies have the potential for future renewable materials, details about structures on different hierarchical levels that span from the nano- to the macroscale are still not unraveled. Rheological characterization is essential for investigating flow properties; however, bulk material properties make it difficult to capture the various length-scales during assembly of the suspensions, for example, in simple shear flow. Rheometry is combined with other characterization methods to allow direct analysis of the structure development in the individual hierarchical levels. While optical techniques, scattering, and spectroscopy are often used to complement rheological observations, coupling them in situ to allow simultaneous observation is paramount to fully understand the details of CNC assembly from liquid to solid. This Review provides an overview of achievements in the coupled analytics, as well as our current opinion about opportunities to unravel the structural distinctiveness of cellulose nanomaterials.

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“…Surprisingly, the successful combination of colloidal LC and gold NPs, in which the suspension would be both mesostructured and coloured, are quite scarce and mostly deal with nanowires rather than nanosheets. [21][22][23][24][25] The strong sensitivity of colloidal LC to ionic strength and molecular additives presumably limits the chemistry that can be employed to obtain a plasmonic colloidal liquid crystal. In this work, we achieved a successful marriage between the colloidal LC host and the gold NP dopant by synthetizing gold NPs at the surface of beidellite clay nanosheets, in-situ, forming a plasmonic clay-based nanocomposite colloid.…”

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confidence: 99%

Gold–clay nanocomposite colloids with liquid-crystalline and plasmonic properties

2021

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SANS study of mixed cholesteric cellulose nanocrystal – gold nanorod suspensions

Abstract: Self-assembly of cellulose nanocrystals (CNCs) doped with anisotropic gold nanorods (AuNRs) was studied by small-angle neutron scattering.

Cited by 14 publications

References 26 publications

Plasmonic Amyloid Tactoids

Plasmonic Amyloid Tactoids

Cellulose Nanocrystal Liquid Crystal Phases: Progress and Challenges in Characterization Using Rheology Coupled to Optics, Scattering, and Spectroscopy

Gold–clay nanocomposite colloids with liquid-crystalline and plasmonic properties

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