Étienne Boulais

Casting inorganic structures with DNA molds.

Introduction The ability to manufacture inorganic nanoparticles (NPs) with arbitrarily prescribed three-dimensional (3D) shapes and positional surface modifications is essential to enabling diverse applications (e.g., in nano-optics and biosensing). However, it is challenging to achieve 3D arbitrary user-specified shapes with sub–5-nm resolution. Top-down lithography has limited resolution, particularly for 3D shapes; capping ligands can be used to tune the energy difference of selected crystallographic facets, but typically only for highly symmetric shapes with identical surface facets. Casting metal particles with prescribed 3D shapes using programmable DNA nanostructure molds. (Top) Schematic of computational shape-by-design framework to encode the user-specified 3D shape of an inorganic particle in the linear sequences of DNA. (Middle) Assembly of the mold and casting growth of the metal particle. (Bottom) Experimental characterization of cast products (transmission electron micrographs; scale bars, 20 nm). Rationale We developed a framework to program arbitrary 3D inorganic NPs using DNA, which serves both as an informational “genome” to encode the 3D shape of a NP and as a physical “fabricator” to retrieve the information and execute the instruction to manufacture the NP. Specifically, our method uses a computationally designed, mechanically stiff synthetic DNA nanostructure with a user-specified cavity as a “mold” to cast the target inorganic NP. The mold encloses a small gold (Au) “seed.” Under mild conditions, the Au seed grows into a larger metal NP that fills the entire cavity, thereby replicating its prescribed 3D shape. The remaining DNA mold additionally acts as a spatially programmable functionalization surface. Results Using this DNA nanocasting method, we constructed three distinct sub–25-nm 3D cuboid silver (Ag) NPs with three independently tunable dimensions. The shape versatility of DNA-based nanocasting was further demonstrated via the synthesis of Ag NPs with equilateral triangular, right triangular, and circular cross sections. The material versatility was demonstrated via synthesis of a Au cuboid in addition to the Ag NPs. The DNA mold served as an addressable coating for the casted NP and thus enabled the construction of higher-order composite structures, including a Y-shaped Ag NP composite and a quantum dot (QD)–Ag-QD sandwiched structure through one-step casting growth. We investigated the key design parameters for stiff DNA molds through mechanical simulations. Multilayered DNA molds provided higher mechanical stiffness for confining NP growth within the mold than single-layer DNA molds, as confirmed by experimental observation. We additionally characterized plasmonic properties of the designer equilateral Ag triangle and Ag sphere through electron energy loss spectroscopy. Tuning of particle symmetry produced a shape-specific spectrum, which is consistent with the predictions of electromagnetism-based simulations. Conclusion DNA nanocasting represents a new framework for the programmable digital fabrication of 3D inorganic nanostructures with prescribed shapes, dimensions, and surface modifications at sub– 5-nm resolution. The key design strategy is to encode linear sequences of DNA with the sophisticated user-specified 3D spatial and surface information of an inorganic NP, as well as to retrieve and execute the information to physically produce this structure via geometric confinement. Such a method may lead to computationally designed functional materials for the digital manufacture of optical nanocircuits, electronic nanocomputers, and perhaps even sophisticated inorganic nanorobots, each with their blueprints (or “genomes’’) encoded in the DNA molecules that constitute their “nanofabricators.” Casting gold and silver with DNA origami Controlling the size and shape of nanoparticles synthesized in solution can be challenging, especially if the goal is to create less symmetric shapes for use in electronic and plasmonic applications. Sun et al. show that DNA “origami”—nanostructures in which the contacts between DNA strands are designed to assemble a particular shape—are sufficiently stiff to act as a mold for the growth of gold and silver nanostructures. The authors created shapes, including a gold particle with a rectangular cross section and a silver triangle with designed plasmonic properties. Science, this issue 10.1126/science.1258361 Shape-tunable metal nanoparticles form by replicating the hollow space inside designed DNA nanostructures. We report a general strategy for designing and synthesizing inorganic nanostructures with arbitrarily prescribed three-dimensional shapes. Computationally designed DNA strands self-assemble into a stiff “nanomold” that contains a user-specified three-dimensional cavity and encloses a nucleating gold “seed.” Under mild conditions, this seed grows into a larger cast structure that fills and thus replicates the cavity. We synthesized a variety of nanoparticles with 3-nanometer resolution: three distinct silver cuboids with three independently tunable dimensions, silver and gold nanoparticles with diverse cross sections, and composite structures with homo- and heterogeneous components. The designer equilateral silver triangular and spherical nanoparticles exhibited plasmonic properties consistent with electromagnetism-based simulations. Our framework is generalizable to more complex geometries and diverse inorganic materials, offering a range of applications in biosensing, photonics, and nanoelectronics.

Off-resonance plasmonic enhanced femtosecond laser optoporation and transfection of cancer cells

A femtosecond laser based transfection method using off-resonance plasmonic gold nanoparticles is described. For human cancer melanoma cells, the treatment leads to a very high perforation rate of 70%, transfection efficiency three times higher than for conventional lipofection, and very low toxicity (<1%). Off-resonance laser excitation inhibited the fracture of the nanoparticles into possibly toxic DNA intercalating particles. This efficient and low toxicity method is a promising alternative to viral transfection for skin cancer treatment.

Plasma Mediated off-Resonance Plasmonic Enhanced Ultrafast Laser-Induced Nanocavitation

The generation of nanobubbles around plasmonic nanostructures is an efficient approach for imaging and therapy, especially in the field of cancer research. We show a novel method using infrared femtosecond laser that generates ≈800 nm bubbles around off-resonance gold nanospheres using 200 mJ/cm(2) 45 fs pulses. We present experimental and theoretical work that demonstrate that the nanobubble formation results from the generation of a nanoscale plasma around the particle due to the enhanced near-field rather than from the heating of the particle. Energy absorbed in the nanoplasma is indeed more than 11 times the energy absorbed in the particle. When compared to the usual approach that uses nanosecond laser to induce the extreme heating of in-resonance nanoparticles to initiate bubble formation, our off-resonance femtosecond technique is shown to bring many advantages, including avoiding the particles fragmentation, working in the optical window of biological material and using the deposited energy more efficiently.

Structure-based model for light-harvesting properties of nucleic acid nanostructures

Programmed self-assembly of DNA enables the rational design of megadalton-scale macromolecular assemblies with sub-nanometer scale precision. These assemblies can be programmed to serve as structural scaffolds for secondary chromophore molecules with light-harvesting properties. Like in natural systems, the local and global spatial organization of these synthetic scaffolded chromophore systems plays a crucial role in their emergent excitonic and optical properties. Previously, we introduced a computational model to predict the large-scale 3D solution structure and flexibility of nucleic acid nanostructures programmed using the principle of scaffolded DNA origami. Here, we use Förster resonance energy transfer theory to simulate the temporal dynamics of dye excitation and energy transfer accounting both for overall DNA nanostructure architecture as well as atomic-level DNA and dye chemical structure and composition. Results are used to calculate emergent optical properties including effective absorption cross-section, absorption and emission spectra and total power transferred to a biomimetic reaction center in an existing seven-helix double stranded DNA-based antenna. This structure-based computational framework enables the efficient in silico evaluation of nucleic acid nanostructures for diverse light-harvesting and photonic applications.

Quantum dot-metallic nanorod sensors via exciton-plasmon interaction.

We investigate quantum nanosensors based on hybrid systems consisting of semiconductor quantum dots and metallic nanorods in the near-infrared regime. These sensors can detect biological and chemical substances based on their impact on the coherent exciton-plasmon coupling and molecular resonances supported by such systems when they interact with a laser field. We demonstrate that the ultrahigh sensitivity of such molecular resonances on environmental conditions allows dramatic and nearly instantaneous changes in the total field experienced by the semiconductor quantum dot via minuscule variations of the local refractive indices of the quantum dot or nanorod. The proposed nanosensors can utilize quantum effects to control the sense (or direction) of the changes in the quantum dot emission, allowing us to have bistable switching from dark to bright states or vice versa via adsorption (or detachment) of biomolecules. These sensors can also offer detection of ultra-small variations in the local dielectric constant of the quantum dots or metallic nanorods via coherent induction of time delays in the effective field experienced by the quantum dots when the hybrid systems interact with time-dependent laser fields. This leads to unprecedented bulk refractive index sensitivities. Our results show that one can utilize quantum phase to control the coherent exciton-plasmon dynamics in these sensors such that introduction of a biomolecule can increase or decrease the time delay. These results offer novel ways to detect single biomolecules via application of quantum coherence to convert their impact into spectacular optical events.

Visible and near infrared resonance plasmonic enhanced nanosecond laser optoporation of cancer cells.

In this paper, we report a light driven, non-invasive cell membrane perforation technique based on the localized field amplification by a nanosecond pulsed laser near gold nanoparticles (AuNPs). The optoporation phenomena is investigated with pulses generated by a Nd:YAG laser for two wavelengths that are either in the visible (532 nm) or near infrared (NIR) (1064 nm). Here, the main objective is to compare on and off localized surface plasmonic resonance (LSPR) to introduce foreign material through the cell membrane using nanosecond laser pulses. The membrane permeability of human melanoma cells (MW278) has been successfully increased as shown by the intake of a fluorescent dye upon irradiation. The viability of this laser driven perforation method is evaluated by propidium iodide exclusion as well as MTT assay. Our results show that up to 25% of the cells are perforated with 532 nm pulses at 50 mJ/cm2 and around 30% of the cells are perforated with 1064 nm pulses at 1 J/cm2. With 532 nm pulses, the viability 2 h after treatment is 64% but it increases to 88% 72 h later. On the other hand, the irradiation with 1064 nm pulses leads to an improved 2 h viability of 81% and reaches 98% after 72 h. Scanning electron microscopy images show that the 5 pulses delivered during treatment induce changes in the AuNPs size distribution when irradiated by a 532 nm beam, while this distribution is barely affected when 1064 nm is used.

Rational Design of Plasmonic Nanoparticles for Enhanced Cavitation and Cell Perforation

Metallic nanoparticles are routinely used as nanoscale antenna capable of absorbing and converting photon energy with subwavelength resolution. Many applications, notably in nanomedicine and nanobiotechnology, benefit from the enhanced optical properties of these materials, which can be exploited to image, damage, or destroy targeted cells and subcellular structures with unprecedented precision. Modern inorganic chemistry enables the synthesis of a large library of nanoparticles with an increasing variety of shapes, composition, and optical characteristic. However, identifying and tailoring nanoparticles morphology to specific applications remains challenging and limits the development of efficient nanoplasmonic technologies. In this work, we report a strategy for the rational design of gold plasmonic nanoshells (AuNS) for the efficient ultrafast laser-based nanoscale bubble generation and cell membrane perforation, which constitute one of the most crucial challenges toward the development of effective gene therapy treatments. We design an in silico rational design framework that we use to tune AuNS morphology to simultaneously optimize for the reduction of the cavitation threshold while preserving the particle structural integrity. Our optimization procedure yields optimal AuNS that are slightly detuned compared to their plasmonic resonance conditions with an optical breakdown threshold 30% lower than randomly selected AuNS and 13% lower compared to similarly optimized gold nanoparticles (AuNP). This design strategy is validated using time-resolved bubble spectroscopy, shadowgraphy imaging and electron microscopy that confirm the particle structural integrity and a reduction of 51% of the cavitation threshold relative to optimal AuNP. Rationally designed AuNS are finally used to perforate cancer cells with an efficiency of 61%, using 33% less energy compared to AuNP, which demonstrate that our rational design framework is readily transferable to a cell environment. The methodology developed here thus provides a general strategy for the systematic design of nanoparticles for nanomedical applications and should be broadly applicable to bioimaging and cell nanosurgery.

Mechanisms of plasmon-enhanced femtosecond laser nanoablation of silicon.

We perform plasmon-enhanced femtosecond laser ablation of silicon using gold nanorods to produce sub-diffraction limit features. While the observed hole shape seems inconsistent with calculated field distribution, we show that using a carrier diffusion-based model, both shape and depth of the nanoholes can be reliably explained. The laser energy is first deposited into electron-hole pairs that are created in the nanostructures enhanced near-field. Those carriers then diffuse and transfer their energy to the silicon lattice, producing ablation. Increased importance of the carrier diffusion process is shown to arise from the extreme localization of the deposited energy around the nanostructure, due to the plasmonic effect. The characteristic shape of holes is revealed as a striking signature of the screened charge carriers-phonon coupling that is shown to channel the heat transfer to the lattice and control ablation.

Coherently-enabled environmental control of optics and energy transfer pathways of hybrid quantum dot-metallic nanoparticle systems

It is well-known that optical properties of semiconductor quantum dots can be controlled using optical cavities or near fields of localized surface plasmon resonances (LSPRs) of metallic nanoparticles. In this paper we study the optics, energy transfer pathways, and exciton states of quantum dots when they are influenced by the near fields associated with plasmonic meta-resonances. Such resonances are formed via coherent coupling of excitons and LSPRs when the quantum dots are close to metallic nanorods and driven by a laser beam. Our results suggest an unprecedented sensitivity to the refractive index of the environment, causing significant spectral changes in the Förster resonance energy transfer from the quantum dots to the nanorods and in exciton transition energies. We demonstrate that when a quantum dot-metallic nanorod system is close to its plasmonic meta-resonance, we can adjust the refractive index to: (i) control the frequency range where the energy transfer from the quantum dot to the metallic nanorod is inhibited, (ii) manipulate the exciton transition energy shift of the quantum dot, and (iii) disengage the quantum dot from the metallic nanoparticle and laser field. Our results show that near meta-resonances the spectral forms of energy transfer and exciton energy shifts are strongly correlated to each other.

Laser-Induced Resistance Fine Tuning of Integrated Polysilicon Thin-Film Resistors

In this brief, we present a novel polysilicon resistor trimming technique using a pulsed focused nanosecond laser at a fluence slightly lower than the melting threshold for polysilicon. Using this technique, we were able to trim a 4 μm ×40 μm Taiwan Semiconductor Manufacturing Company 180-nm n-doped polysilicon resistors with a 200-ppm precision. Much better precision is possible by using larger structures. The method can be applied to any CMOS process without any extra layer deposition or specific design restriction beside the fact that the laser beam must be able to reach the polysilicon structure. The high repeatability of the process allows an open-loop calibration. A complete characterization of the trimmed devices, including transverse electromagnetic and atomic force microscopy imaging as well as Raman spectroscopy, has been conducted, leading to the conclusion that a material restructuration in the grain boundaries of polysilicon, following laser irradiation, is responsible for the thin-film resistivity lowering. The stability of the polysilicon thin film, as tested by heating the device at 150°C during 1000 h, is about 1.3%, which is slightly higher than the 0.7% resistance variation for untrimmed thin films.