Non-Invasive, Reliable, and Fast Quantification of DNA Loading on Gold Nanoparticles by a One-Step Optical Measurement

An exquisite, versatile, and reproducible quantification of DNA loading on gold nanoparticles (Au NPs) has long been pursued because this loading influences the analytical, therapeutic, and self-assembly behaviors of DNA-Au NPs. Nevertheless, the existing methods used thus far rely solely on the invasive detachment and subsequent spectroscopic quantification of DNA, which are error-prone and highly dependent on trained personnel. Here, we present a non-invasive optical framework that can determine the number of DNA strands on Au NPs by versatile one-step measurement of the visible absorption spectra of DNA-Au NP solutions without any invasive modifications or downstream processes. Using effective medium theory in conjunction with electromagnetic numerical calculation, the change in DNA loading density, resulting from varying the ion concentration, Au NP size, DNA strand length, and surrounding temperature, can be tracked in situ merely by the one-step measurement of visible absorption spectra, which is otherwise impossible to achieve. Moreover, the simplicity and robustness of this method promote reproducible DNA loading quantification regardless of experimental adeptness, which is in stark contrast with existing invasive and multistep methods. Overall, the optical framework outlined in this work can contribute to democratizing research on DNA-Au NPs and facilitating their rapid adoption in transformative applications

Non-Invasive, Reliable, and Fast Quantification of DNA Loading on Gold Nanoparticles by a One-Step Optical Measurement

An exquisite, versatile, and reproducible quantification of DNA loading on gold nanoparticles (Au NPs) has long been pursued because this loading influences the analytical, therapeutic, and self-assembly behaviors of DNA-Au NPs. Nevertheless, the existing methods used thus far rely solely on the invasive detachment and subsequent spectroscopic quantification of DNA, which are error-prone and highly dependent on trained personnel. Here, we present a non-invasive optical framework that can determine the number of DNA strands on Au NPs by versatile one-step measurement of the visible absorption spectra of DNA-Au NP solutions without any invasive modifications or downstream processes. Using effective medium theory in conjunction with electromagnetic numerical calculation, the change in DNA loading density, resulting from varying the ion concentration, Au NP size, DNA strand length, and surrounding temperature, can be tracked in situ merely by the one-step measurement of visible absorption spectra, which is otherwise impossible to achieve. Moreover, the simplicity and robustness of this method promote reproducible DNA loading quantification regardless of experimental adeptness, which is in stark contrast with existing invasive and multistep methods. Overall, the optical framework outlined in this work can contribute to democratizing research on DNA-Au NPs and facilitating their rapid adoption in transformative applications

Plasmonic Metamaterial Perovskite Solar Cells: Fundamental Tradeoffs, Limitations, and Opportunities

Whether dispersal of plasmonic nanoparticles (NPs) within a perovskite active layer can increase the efficiency of solar cells is a long-standing question. It is well known that inclusion of metallic NPs in an active layer can boost the surrounding near-field intensity around them owing to the dipolar localized surface plasmon resonance (LSPR, also called antenna effect), which can increase light absorption by solar cells. However, the use of plasmonic NPs in perovskite solar cells has been barely reported, and it is not known whether inserting plasmonic NPs into a perovskite active layer produces any performance advantage compared with a pure perovskite counterpart. We explore the fundamental and practical limits of plasmonic metamaterial perovskite solar cells by applying effective medium theory and a detailed balance analysis. Our results indicate that an increase in effective refractive index of perovskite through dispersed plasmonic NPs can in principle enhance the performance of solar cells

Soft Plasmonic Assemblies Exhibiting Unnaturally High Refractive Index

The increases in refractive indices (n) of materials are crucial for transformative optical technologies. With the progress of monolithic lithography, large advances have been achieved with several semiconductors, including silicon, germanium, and gallium arsenide, which generally provide higher n of ∼4.0 compared to those of other elements. Nevertheless, above this upper limit of naturally available n, the range of light–matter interactions could be unprecedentedly expanded, which in turn enriches the possible applications. Here, we present a soft self-assembly of polyhedral Au colloids as a promising method to achieve unnaturally high n values. The interfacial assembly of Au nanocubes provides n of 6.4 at the resonant wavelength (near-infrared) and 4.5 in the off-resonant regimes (mid-infrared), which have not been previously reached. The soft self-assembly of polyhedral Au colloids can be a versatile and highly effective route for the fabrication of optical metamaterials with unnaturally high n values

Surface potential-driven surface states in 3D topological photonic crystals

Surface potential in a topological matter could unprecedentedly localize the waves. However, this surface potential is yet to be exploited in topological photonic systems. Here, we demonstrate that photonic surface states can be induced and controlled by the surface potential in a dielectric double gyroid (DG) photonic crystal. The basis translation in a unit cell enables tuning of the surface potential, which in turn regulates the degree of wave localization. The gradual modulation of DG photonic crystals enables the generation of a pseudomagnetic field. Overall, this study shows the interplay between surface potential and pseudomagnetic field regarding the surface states. The physical consequences outlined herein not only widen the scope of surface states in 3D photonic crystals but also highlight the importance of surface treatments in a photonic system

Design of DNA Origami Diamond Photonic Crystals

Self-assembled photonic crystals have proven to be a fascinating class of photonic materials for nonabsorbing structural colorizations over large areas and in diverse relevant applications, including tools for on-chip spectrometers and biosensors, platforms for reflective displays, and templates for energy devices. The most prevalent building blocks for the self-assembly of photonic crystals are spherical colloids and block copolymers (BCPs) because of the generic appeal of these materials, which can be crafted into large-area 3D lattices. However, because of the intrinsic limitations of these structures, these two building blocks are difficult to assemble into a direct rod-connected diamond lattice, which is considered to be a champion photonic crystal. Here, we present a DNA origami-route for a direct rod-connected diamond photonic crystal exhibiting a complete photonic bandgap (PBG) in the visible regime. Using a combination of electromagnetic, phononic, and mechanical numerical analyses, we identify (i) the structural constraints of the 50 megadalton-scale giant DNA origami building blocks that could self-assemble into a direct rod-connected diamond lattice with high accuracy, and (ii) the elastic moduli that are essentials for maintaining lattice integrity in a buffer solution. A solution molding process could enable the transformation of the as-assembled DNA origami lattice into a porous silicon- or germanium-coated composite crystal with enhanced refractive index contrast, in that a champion relative bandwidth for the photonic bandgap (i.e., 0.29) could become possible even for a relatively low volume fraction (i.e., 16 vol %)

Fabrication of the Funnel-Shaped Three-Dimensional Plasmonic Tip Arrays by Directional Photofluidization Lithography

Plasmonics allow localization of an electromagnetic (EM) field into nanoscale “hotspots”, a feature that is of technological significance due to potential applications related to spectroscopic sensing and nanofocusing. In relation to this, many researchers have sought to fabricate metallic nanostructures with sharp edges, as they provide much higher EM field enhancement compared with rounded structures. However, a fabrication method satisfying stringent requirements for the efficient EM field enhancement including three-dimensionality, vertical orientation, large-area fabrication, and tunability of structural features, which are of practical importance for efficient plasmonic light enhancement at hotspots, has yet to be achieved. Herein, we fabricate large-area, vertically aligned three-dimensional plasmonic tip (i.e., nanofunnel) arrays with unprecedented flexibility in the control of the structural features by directional photofluidization lithography. Using this approach, the structural features of nanofunnel tips including the sharpness, shape, and orientation were precisely controlled in a scalable and deterministic manner. The effects of the structural features of the nanofunnel on the EM field enhancement were systematically investigated and analyzed, and the optimum tip features for maximum EM field enhancement were thereupon identified. The suggested nanofabrication technique and resulting structures will be of practical importance in spectroscopic and nanophotonic applications

Practical Limits of Achieving Artificial Magnetism and Effective Optical Medium by Using Self-Assembly of Metallic Colloidal Clusters

The self-assembly of metallic colloidal clusters (so called plasmonic metamolecules) has been viewed as a versatile, but highly effective approach for the materialization of the metamaterials exhibiting artificial magnetism at optical frequencies (including visible and near infrared (NIR) regimes). Indeed, several proofs of concepts of plasmonic metamolecules have been successfully demonstrated in both theoretical and experimental ways. Nevertheless, this self-assembly strategy has barely been used and still remains an underutilized method. For example, the self-assembly and optical utilization of the plasmonic metamolecules have been limited to the discrete unit of the structure; the materialization of effective optical medium made of plasmonic metamolecules is highly challenging. In this work, we theoretically exploited the practical limits of self-assembly technology for the fabrication of optical magnetic metamaterials

Antifreezing Gold Colloids

Gold (Au) colloids are becoming ubiquitous across biomedical engineering, solar energy conversion, and nano-optics. Such universality has originated from the exotic plasmonic effect of Au colloids (i.e., localized surface plasmon resonance (LSPRs)) in conjunction with the versatile access to their synthetic routes. Herein, we introduce a previously undiscovered usage of Au colloids for advancing cryoprotectants with significant ice recrystallization inhibition (IRI). Oligopeptides inspired by the antifreeze protein (AFP) and antifreeze glycoprotein (AFGP) are attached onto the surface of well-defined Au colloids with the same sizes but different shapes. These AF­(G)­P-inspired Au colloids can directly adsorb onto a growing ice crystal via the synergistic interplay between hydrogen bonding and hydrophobic groups, in stark contrast to their bare Au counterparts. Dark-field optical microscopy analyses, benefiting from LSPR, allow us to individually trace the in situ movement of the antifreezing Au colloids during ice growth/recrystallization and clearly evidence their direct adsorption onto the growing ice crystal, which is consistent with theoretical predictions. With the assistance of molecular dynamics (MD) simulations, we evidently attribute the IRI of AF­(G)­P-inspired Au colloids to the Kelvin effect. We also exploit the IRI dependence on the Au colloidal shapes; indeed, the facet contacts between ice and Au colloids can be better than the point-like counterparts in terms of IRI. The design principles and predictive theory outlined in this work will be of broad interest not only for the fundamental exploration of the inhibition of ice growth but also for enriching the application of Au colloids

Baseline characteristics of the study subjects.

Baseline characteristics of the study subjects.</p