Welded Gold Nanoparticle Assemblies Defined Plasmonic Coupling.

Nanoparticle assemblies with interparticle ohmic contacts are crucial for nanodevice fabrication. Despite tremendous progress in DNA-programmable nanoparticle assemblies, seamlessly welding discrete components into welded continuous three-dimensional (3D) configurations remains challenging. Here, we introduce a single-stranded DNA-encoded strategy to customize welded metal nanostructures with tunable morphologies and plasmonic properties. We demonstrate the precise welding of gold nanoparticle assemblies into continuous metal nanostructures with interparticle ohmic contacts through chemical welding in solution. We find that the welded gold nanoparticle assemblies show a consistent morphology with welded efficiency over 90%, such as the rod-like, triangular, and tetrahedral metal nanostructures. Next, we show the versatility of this strategy by welding gold nanoparticle assemblies of varied sizes and shapes. Furthermore, the experiment and simulation show that the welded gold nanoparticle assemblies exhibit defined plasmonic coupling. This single-stranded DNA encoded welding system may provide a new route for accurately building functional plasmonic nanomaterials and devices.

Nanoparticle Assembly in High Polymer Concentration Solutions Increases Superlattice Stability.

Polymer nanocomposites are made by combining a nanoscale filler with a polymer matrix, where polymer-particle interactions can enhance matrix properties and introduce behaviors distinct from either component. Manipulating particle organization within a composite potentially allows for better control over polymer-particle interactions, and the formation of ordered arrays can introduce new, emergent properties not observed in random composites. However, self-assembly of ordered particle arrays typically requires weak interparticle interactions to prevent kinetic traps, making these assemblies incompatible with most conventional processing techniques. As a result, more fundamental investigations are needed into methods to provide additional stability to these lattices without disrupting their internal organization. The authors show that the addition of free polymer chains to the assembly solution is a simple means to increase the stability of nanoparticle superlattices against thermal dissociation. By adding high concentrations (>50 mg mL-1 ) of free polymer to nanoparticle superlattices, it is possible to significantly elevate their thermal stability without adversely affecting ordering. Moreover, polymer topology, molecular weight, and concentration can also be used as independent design handles to tune this behavior. Collectively, this work allows for a wider range of processing conditions for generating future nanocomposites with complete control over particle organization within the material.

Directed Nanoparticle Assembly through Polymer Crystallization.

Nanoparticles can be assembled into complex structures and architectures by using a variety of methods. In this review, we discuss recent progress of using polymer crystallization (particularly polymer single crystals, PSCs) to direct nanoparticle assembly. PSCs have been extensively studied since 1957. Mainly appearing as quasi-two-dimensional (2D) lamellae, PSCs are typically used as model systems to determine polymer crystalline structures, or as markers to investigate the crystallization process. Recent research has demonstrated that they can also be used as nanoscale functional materials. Herein, we show that nanoparticles can be directed to assemble into complex shapes by using in situ or ex situ polymer crystal growth. End-functionalized polymers can crystallize into 2D nanosheet PSCs, which are used to conjugate with complementary nanoparticles, leading to a nanosandwich structure. These nanosandwiches can find interesting applications for catalysis, surface-enhanced Raman spectroscopy, and nanomotors. Dissolution of the nanosandwich leads to the formation of Janus nanoparticles, providing a unique method for asymmetric nanoparticle synthesis.

Shape-tailored polymer colloids on the road to become structural motifs for hierarchically organized materials.

Anisometric polymer colloids are likely to behave differently when compared with centrosymmetric particles. Their study may not only shine new light on the organization of matter; they may also serve as building units with specific symmetries and complexity to build new materials from them. Polymer colloids of well-defined complex geometries can be obtained by packing a limited number of spherical polymer particles into clusters with defined configurations. Such supracolloidal architectures can be fabricated at larger scales using narrowly dispersed emulsion droplets as templates. Assemblies built from at least two different types of particles as elementary building units open perspectives in selective targeting of colloids with specific properties, aiming for mesoscale building blocks with tailor-made morphologies and multifunctionality. Polymer colloids with defined geometries are also ideal to study shape-dependent properties such as the diffusion of complex particles.

Open and Close-Packed, Shape-Engineered Polygonal Nanoparticle Metamolecules with Tailorable Fano Resonances.

A top-down lithographic patterning and deposition process is reported for producing nanoparticles (NPs) with well-defined sizes, shapes, and compositions that are often not accessible by wet-chemical synthetic methods. These NPs are ligated and harvested from the substrate surface to prepare colloidal NP dispersions. Using a template-assisted assembly technique, fabricated NPs are driven by capillary forces to assemble into size- and shape-engineered templates and organize into open or close-packed multi-NP structures or NP metamolecules. The sizes and shapes of the NPs and of the templates control the NP number, coordination, interparticle gap size, disorder, and location of defects such as voids in the NP metamolecules. The plasmonic resonances of polygonal-shaped Au NPs are exploited to correlate the structure and optical properties of assembled NP metamolecules. Comparing open and close-packed architectures highlights that introduction of a center NP to form close-packed assemblies supports collective interactions, altering magnetic optical modes and multipolar interactions in Fano resonances. Decreasing the distance between NPs strengthens the plasmonic coupling, and the structural symmetries of the NP metamolecules determine the orientation-dependent scattering response.

Self-Assembly of Plasmonic Nanoantenna-Waveguide Structures for Subdiffractional Chiral Sensing.

Spin-momentum locking is a peculiar effect in the near-field of guided optical or plasmonic modes. It can be utilized to map the spinning or handedness of electromagnetic fields onto the propagation direction. This motivates a method to probe the circular dichroism of an illuminated chiral object. In this work, we demonstrate local, subdiffraction limited chiral coupling of light and propagating surface plasmon polaritons in a self-assembled system of a gold nanoantenna and a silver nanowire. A thin silica shell around the nanowire provides precise distance control and also serves as a host for fluorescent molecules, which indicate the direction of plasmon propagation. We characterize our nanoantenna-nanowire systems comprehensively through correlated electron microscopy, energy-dispersive X-ray spectroscopy, dark-field, and fluorescence imaging. Three-dimensional numerical simulations support the experimental findings. Besides our measurement of far-field polarization, we estimate sensing capabilities and derive not only a sensitivity of 1 mdeg for the ellipticity of the light field, but also find 103 deg cm2/dmol for the circular dichroism of an analyte locally introduced in the hot spot of the antenna-wire system. Thorough modeling of a prototypical design predicts on-chip sensing of chiral analytes. This introduces our system as an ultracompact sensor for chiral response far below the diffraction limit.

Enzyme-Responsive Ag Nanoparticle Assemblies in Targeting Antibacterial against Methicillin-Resistant Staphylococcus Aureus.

The abuse of antibiotics resulted in the emergence of antibiotics-resistant bacteria, which has raised a great social concern together with the impetus to develop effective antibacterial materials. Herein, the synthesis of biocompatible enzyme-responsive Ag nanoparticle assemblies (ANAs) and their application in the high-efficiency targeted antimicrobial treatment of methicillin-resistant Staphylococcus aureus (MRSA) have been demonstrated. The ANAs could collapse and undergo stable/collapsed transition on approaching MRSA because of the serine protease-like B enzyme proteins (SplB)-triggered decomposition of the branched copolymers which have been employed as the macrotemplate in the synthesis of responsive ANAs. This transition contributed greatly to the high targeting affinity and efficiency of ANAs to MRSA. The minimum inhibitory concentration and minimum bactericidal concentration against MRSA were 2.0 and 32.0 µg mL-1, respectively. Skin wound healing experiments confirmed that the responsive ANAs could serve as an effective wound dressing to accelerate the healing of MRSA infection.

Hierarchical Nanoparticle Assemblies Formed via One-Step Catalytic Stamp Pattern Transfer.

The one-step catalytic stamp pattern transfer process is described for producing arrays of hierarchical nanoparticle assemblies. The method simply combines in situ nanoparticle synthesis triggered by free residual Si-H groups on PDMS stamps and the lift-off pattern transfer technique. No additional nanoparticle synthesis procedure is required before the pattern transfer process. Exquisitely uniform and precisely spaced hierarchical nanoparticle assemblies with designed geometry can be rapidly produced using the catalytic stamp pattern transfer process. Sequential catalytic stamp pattern transfer also is described to generate multilayered, hierarchical nanoparticle assemblies with various geometries. The hierarchical nanoparticle assemblies catalytically transferred onto the surface are not just nanoparticles but nanoparticle-polydimethylsiloxane residue composites. The in situ-synthesized nanoparticles retain optical properties. The hierarchical nanoparticle assemblies with precisely controlled geometry further show potential in the application of surface-enhanced Raman scattering. The capability of one-step catalytic stamp pattern transfer allows the scalable and reproducible fabrication of well-defined hierarchical nanoparticle assemblies.

Modifying Thermal Switchability of Liquid Crystalline Nanoparticles by Alkyl Ligands Variation.

By coating plasmonic nanoparticles (NPs) with thermally responsive liquid crystals (LCs) it is possible to prepare reversibly reconfigurable plasmonic nanomaterials with prospective applications in optoelectronic devices. However, simple and versatile methods to precisely tailor properties of liquid-crystalline nanoparticles (LC NPs) are still required. Here, we report a new method for tuning structural properties of assemblies of nanoparticles grafted with a mixture of promesogenic and alkyl thiols, by varying design of the latter. As a model system, we used Ag and Au nanoparticles that were coated with three-ring promesogenic molecules and dodecanethiol ligand. These LC NPs self-assemble into switchable lamellar (Ag NPs) or tetragonal (Au NPs) aggregates, as determined with small angle X-ray diffraction and transmission electron microscopy. Reconfigurable assemblies of Au NPs with different unit cell symmetry (orthorombic) are formed if hexadecanethiol and 1H,1H,2H,2H-perfluorodecanethiol were used in the place of dodecanethiol; in the case of Ag NPs the use of 11-hydroxyundecanethiol promotes formation of a lamellar structure as in the reference system, although with substantially broader range of thermal stability (140 vs. 90 °C). Our results underline the importance of alkyl ligand functionalities in determining structural properties of liquid-crystalline nanoparticles, and, more generally, broaden the scope of synthetic tools available for tailoring properties of reversibly reconfigurable plasmonic nanomaterials.

Tuning the Sensing Performance of Multilayer Plasmonic Core-Satellite Assemblies for Rapid Detection of Targets from Lysed Cells.

Optical sensors based on discrete plasmonic nanostructures are invaluable for probing biomolecular interactions when applied as plasmonic rulers or reconfigurable multinanoparticle assemblies. However, their adaptation as a versatile sensing platform is limited by the research-grade instrumentation required for single-nanostructure imaging and/or spectroscopy and complex data fitting and analysis. Additionally, the dynamic range is often too narrow for the quantitative analysis of targets of interest in biodiagnostics, food safety, or environmental monitoring. Herein we present plasmonic assembly comprising a core nanoparticle surrounded by multiple layers of satellite nanoparticles through aptamer linker. The layer-by-layer assembly of the satellite nanoparticles yields uniform discrete nanoparticle clusters on a substrate with enhanced optical properties. Binding of the model target (adenosine 5'-triphosphate, ATP) induces disassembly and leads to a dramatic decrease in the scattering intensity that can be analyzed readily from darkfield images. We demonstrate that the sensing performance, such as detection limit, dynamic range, and sensitivity, can be tuned by controlling the size of the assembly. The substrate-anchored nanoparticle assemblies are selective to only ATP, and not other adenine-containing compounds. By adapting the methodology to a flexible support, cellular ATP can be directly detected by lysing adherent cells in close contact with the plasmonic assemblies-a process that does not require any sample preparation or purification. Enhancing the optical detection signal via designing and engineering nanoparticle assemblies could enable their use with low-cost portable imaging systems and broaden their applicability beyond the study of biomolecular interaction.

Surface engineering of Solid Lipid Nanoparticle assemblies by methyl α-d-mannopyranoside for the active targeting to macrophages in anti-tuberculosis inhalation therapy.

This study describes the development of new mannosylated Solid Lipid Nanoparticle assemblies (SLNas) delivering rifampicin for an inhaled treatment of tuberculosis. SLNas were surface engineered with mannose residues to recognize mannose receptors located on infected alveolar macrophages and facilitate cell internalization. Two sets of SLNas were produced by the melt emulsifying technique using biocompatible lipid components, i.e. cholesteryl myristate combined with palmitic acid (PA set) or tripalmitin (TP set), in the presence of the targeting moiety, methyl α-d-mannopyranoside. Mannosylated SLNas were examined for their physical properties, drug payloads and release, as well as respirability in terms of emitted dose and respirable fraction determined by Next Generation Impactor. The most appropriate formulations were assessed for mannosylation using FTIR, XPS, SEM coupled with EDX analysis, and wettability assay, in comparison with the respective non-functionalized SLNas. Besides, cytotoxicity and cell internalization ability were established on J774 murine macrophage cell line. Mannosylated SLNas exhibited physical properties suitable for alveolar macrophage passive targeting, adequate rifampicin payloads (10-15%), and feasible drug maintenance within SLNas along the respiratory tract before macrophage internalization. Despite respirability impaired by powder cohesiveness, surface mannosylation provided quicker macrophage phagocytosis, giving evidence of an active targeting promotion.

Nanoparticle Clusters: Assembly and Control Over Internal Order, Current Capabilities, and Future Potential.

The current state of the art in the use of colloidal methods to form nanoparticle assemblies, or clusters (NPCs) is reviewed. The focus is on the two-step approach, which exploits the advantages of bottom-up wet chemical NP synthesis procedures, with subsequent colloidal destabilization to trigger assembly in a controlled manner. Recent successes in the application of functional NPCs with enhanced emergent collective properties for a wide range of applications, including in biomedical detection, surface enhanced Raman scattering (SERS) enhancement, photocatalysis, and light harvesting, are highlighted. The role of the NP-NP interactions in the formation of monodisperse ordered clusters is described and the different assembly processes from a wide range of literature sources are classified according to the nature of the perturbation from the initial equilibrium state (dispersed NPs). Finally, the future for the field and the anticipated role of computational approaches in developing next-generation functional NPCs are briefly discussed.

Nanoparticle Assemblies: Nanoparticle Clusters: Assembly and Control Over Internal Order, Current Capabilities, and Future Potential (Adv. Mater. 27/2016).

Clusters or assemblies of nanoparticles exhibit unique features which arise from the enhancement of properties of single nanoparticles or due to new collective properties. On page 5400, D. F. Brougham and co-workers review the role of nanoparticle interactions in controlling cluster formation, and classify the assembly mechanisms. Emerging applications for surface-enhanced Raman scattering (SERS), optical labeling, light harvesting, magnetic resonance imaging (MRI), hyperthermia, photocatalysis, enrichment, and separation are presented. Cover image by Christoph Hohmann, Nanosystems Initiative Munich (NIM).

Electron Energy Loss Spectroscopy Investigation into Symmetry in Gold Trimer and Tetramer Plasmonic Nanoparticle Structures.

We present a combined scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) investigation into the mode symmetries of plasmonic nanoparticle trimer and tetramer structures. We obtain nanometer-resolved energy loss spectra for both trimer and tetramer structures and compare these to boundary element method simulations. We show that EELS, in conjunction with eigenmode simulations, offers a complete characterization of the individual superstructures, and we trace the evolution of both optically dark and bright modes and identify multipolar mode contributions. We then apply this technique to tetramer structures that exhibit an expanded range of mode symmetries for two-dimensional and three-dimensional self-assembled geometries. These findings provide a comprehensive experimental account of the available photonic states in self-assembled nanoparticle clusters.

Au(I)-thiolate nanostructures fabricated by chemical exfoliation and their transformation to gold nanoparticle assemblies.

Chemical exfoliation method was applied to transform bulky assemblies of Au(I)-3-mercaptopropionate (MPA) coordination polymer (CP) to nanosheets and nanostrings using sodium citrate as an exfoliator. The exfoliation process and the structural characteristics of the Au(I)-MPA nanosheets and nanostrings were fully investigated by transmission electron microscopy, atomic force microscopy, UV-vis absorption spectroscopy, X-ray photoelectron spectroscopy and so on. As the structural rigidity and stability of the obtained Au(I)-MPA nanosheets, they are ideal precursors for fabrication of water soluble gold nanoparticle assemblies through progressive pyrolysis. This work provides a significant strategy toward the morphology regulation of CP nanostructures and will inspire further development of this research area.