Non-lithographic SERS substrates: tailoring surface chemistry for Au nanoparticle cluster assembly

Near‐field plasmonic coupling and local field enhancement in metal nanoarchitectures, such as arrangements of nanoparticle clusters, have application in many technologies from medical diagnostics, solar cells, to sensors. Although nanoparticle‐based cluster assemblies have exhibited signal enhancements in surface‐enhanced Raman scattering (SERS) sensors, it is challenging to achieve high reproducibility in SERS response using low‐cost fabrication methods. Here an innovative method is developed for fabricating self‐organized clusters of metal nanoparticles on diblock copolymer thin films as SERS‐active structures. Monodisperse, colloidal gold nanoparticles are attached via a crosslinking reaction on self‐organized chemically functionalized poly(methyl methacrylate) domains on polystyrene‐block‐poly(methyl methacrylate) templates. Thereby nanoparticle clusters with sub‐10‐nanometer interparticle spacing are achieved. Varying the molar concentration of functional chemical groups and crosslinking agent during the assembly process is found to affect the agglomeration of Au nanoparticles into clusters. Samples with a high surface coverage of nanoparticle cluster assemblies yield relative enhancement factors on the order of 10⁹ while simultaneously producing uniform signal enhancements in point‐to‐point measurements across each sample. High enhancement factors are associated with the narrow gap between nanoparticles assembled in clusters in full‐wave electromagnetic simulations. Reusability for small‐molecule detection is also demonstrated. Thus it is shown that the combination of high signal enhancement and reproducibility is achievable using a completely non‐lithographic fabrication process, thereby producing SERS substrates having high performance at low cost.     

Formation of 1D and 2D gold nanoparticle arrays by divalent DNA-gold nanoparticle conjugates

Divalent DNA-AuNP (gold nanoparticle) conjugates comprising two DNA strands at diametrically opposed positions are prepared. Highly linear 1D and tetragonal lattice-like 2D AuNP arrays are constructed using the conjugates and DNA assemblies based on T- and double-crossover motifs and the Holliday junction.     

Controlling nanoparticle location via confined assembly in electrospun block copolymer nanofibers

Coaxial nanofibers with poly(styrene-block-isoprene) (PS-b-PI)/magnetite nanoparticles as core and silica as shell are fabricated using electrospinning.1-4 Thermally stable silica helps to anneal the fibers above the glass transition temperature of PS-b-PI and form ordered nanocomposite morphologies. Monodisperse magnetite nanoparticles (NPs; 4 nm) are synthesized and surface coated with oleic acid to provide marginal selectivity towards an isoprene domain. When 4 wt% nanoparticles are added to symmetric PS-b-PI, transmission electron microscopy (TEM) images of microtomed electrospun fibers reveal that NPs are uniformly dispersed only in the PI domain, and that the confined lamellar assembly in the form of alternate concentric rings of PS and PI is preserved. For 10 wt% NPs, a morphology transition is seen from concentric rings to a co-continuous phase with NPs again uniformly dispersed in the PI domains. No aggregates or loss of PI selectivity is found in spite of interparticle attraction. Magnetic properties are measured using a superconducting quantum interference device (SQUID) magnetometer and all nanocomposite fiber samples exhibit superparamagnetic behavior.     

Interparticle Forces Underlying Nanoparticle Self‐Assemblies

Studies on the self‐assembly of nanoparticles have been a hot topic in nanotechnology for decades and still remain relevant for the present and future due to their tunable collective properties as well as their remarkable applications to a wide range of fields. The novel properties of nanoparticle assemblies arise from their internal interactions and assemblies with the desired architecture key to constructing novel nanodevices. Therefore, a comprehensive understanding of the interparticle forces of nanoparticle self‐assemblies is a pre‐requisite to the design and control of the assembly processes, so as to fabricate the ideal nanomaterial and nanoproducts. Here, different categories of interparticle forces are classified and discussed according to their origins, behaviors and functions during the assembly processes, and the induced collective properties of the corresponding nanoparticle assemblies. Common interparticle forces, such as van der Waals forces, electrostatic interactions, electromagnetic dipole‐dipole interactions, hydrogen bonds, solvophonic interactions, and depletion interactions are discussed in detail. In addition, new categories of assembly principles are summarized and introduced. These are termed template‐mediated interactions and shape‐complementary interactions. A deep understanding of the interactions inside self‐assembled nanoparticles, and a broader perspective for the future synthesis and fabrication of these promising nanomaterials is provided.     

Versatile preparation of fluorescent particles based on polyphosphazenes: from micro- to nanoscale

A series of intrinsically fluorescent hydrophobic and amphiphilic polyphosphazenes with ethyl tryptophan (EtTrp) and poly(N-isopropylacrylamide) (PNIPAAm) or poly(ethylene glycol) (PEG) as hydrophobic and hydrophilic segments, respectively, are synthesized. Depending on polymer composition and preparation procedure, particles with diameters ranging from micro- to nanoscale can be prepared successfully, which might be used as a visible tracer, both in vitro or in vivo, in drug- or gene-delivery systems, as well as in other biomedical studies such as diagnostic medicine and brain research. Most importantly, in combination with the flexible synthesis and versatile modification of polyphosphazene, this method provides a general protocol to engineer a broad range of fluorescent particles with different properties based on diverse polymers.     

Controlled assembly of spherical nanoparticles: nanowires and spherulites

A large variety of nanoparticles hold extraordinary promise for practical applications in catalysis, materials science, medicine, and so on. It is, however, necessary to assemble them into supramolecular aggregates with desired structural properties. In this work we explore the self-assembly of spherical nanoparticles induced by interactions that, due to entropic effects, may become anisotropic. The spherical nanoparticles considered attract each other via square-well potentials, mimicking dispersive interactions. To induce anisotropic effects, short polymer brushes are bound to the nanoparticles but only on the equatorial plane. The brushes are treated as tangent-hard-sphere chains. Nanoparticles with such morphology could be synthesized experimentally. Monte Carlo calculations are conducted to assess the properties of the self-assembled nanostructures as a function of the length of the brushes and of the depth of the particle-particle square-well potential. Our results indicate that for strongly attractive particle-particle interactions it is possible to obtain supramolecular spherulites (employing short brushes) or uniform dispersions (using long brushes). At some intermediate lengths of the polymer brushes, the formation of one-dimensional wires occurs. Our results are useful for designing responsive nanoparticles that reversibly assemble yielding uniform dispersions, nanowires, or spherulites depending on the solution conditions.     

Design and application of inorganic nanoparticle superstructures: current status and future challenges

Self-assembly of inorganic nanoparticles (NPs) into superstructures, which is used as a general way to integrate functional inorganic NPs into macroscale devices, has attracted much research interest. This review will summarize the recent progress and discuss future challenges of the inorganic NP superstructures. Examples include both DNA-based and polymer-based NP assemblies with controlled positioning and geometries, and quasicrystalline ordered structures from the self-assembly of binary or ternary NPs. Different from their individual NP counterparts, these self-assembled superstructures possess unique properties, such as optical chirality and dynamic structural change under an external stimulus. Due to their diversified structures and functionalities, inorganic NP superstructures have shown a wide range of promise for applications in electronic and photonic devices, such as field-effect transistors, magnetoresistive components, optical information recording, and solar cells.     

Controlled arrangement of nanoparticle arrays in block-copolymer domains

This Review describes recent results on the precise spatial distribution control of metal and semiconductor nanoparticles into domains of microphase-separated block copolymers. Specific focus is directed towards selective incorporation into a specific microphase of a block copolymer. Details on theoretical aspects concerning nanoparticle incorporation as well as practical examples are given. Furthermore, examples on applications and technological aspects of the resulting nanoparticle/polymer nanocomposites are provided.     

In‐Plane Direct‐Write Assembly of Iridescent Colloidal Crystals

Materials made by directed self‐assembly of colloids can exhibit a rich spectrum of optical phenomena, including photonic bandgaps, coherent scattering, collective plasmonic resonance, and wave guiding. The assembly of colloidal particles with spatial selectivity is critical for studying these phenomena and for practical device fabrication. While there are well‐established techniques for patterning colloidal crystals, these often require multiple steps including the fabrication of a physical template for masking, etching, stamping, or directing dewetting. Here, the direct‐writing of colloidal suspensions is presented as a technique for fabrication of iridescent colloidal crystals in arbitrary 2D patterns. Leveraging the principles of convective assembly, the process can be optimized for high writing speeds (≈600 µm s^?1) at mild process temperature (30 °C) while maintaining long‐range (cm‐scale) order in the colloidal crystals. The crystals exhibit structural color by grating diffraction, and analysis of diffraction allows particle size, relative grain size, and grain orientation to be deduced. The effect of write trajectory on particle ordering is discussed and insights for developing 3D printing techniques for colloidal crystals via layer‐wise printing and sintering are provided.     

The role of defects on the assembly and stability of DNA nanostructures

Defects are known to underlie the mechanical properties of materials, especially so at the nanoscale. Using four compositionally identical DNA triangles, defect density is found to be inversely correlated with assembly efficiency and melting temperature. These findings are supported by a series of experiments with more complex DNA pyramids. Because they are naturally responsive to stresses, defects present an attractive opportunity as design elements for responsive DNA materials.     

Design, assembly, and activity of antisense DNA nanostructures

Discrete DNA nanostructures allow simultaneous features not possible with traditional DNA forms: encapsulation of cargo, display of multiple ligands, and resistance to enzymatic digestion. These properties suggested using DNA nanostructures as a delivery platform. Here, DNA pyramids displaying antisense motifs are shown to be able to specifically degrade mRNA and inhibit protein expression in vitro, and they show improved cell uptake and gene silencing when compared to linear DNA. Furthermore, the activity of these pyramids can be regulated by the introduction of an appropriate complementary strand. These results highlight the versatility of DNA nanostructures as functional devices.     

Magnetic Plasmon Networks Programmed by Molecular Self‐Assembly

Nanoscale manipulation of magnetic fields has been a long‐term pursuit in plasmonics and metamaterials, as it can enable a range of appealing optical properties, such as high‐sensitivity circular dichroism, directional scattering, and low‐refractive‐index materials. Inspired by the natural magnetism of aromatic molecules, the cyclic ring cluster of plasmonic nanoparticles (NPs) has been suggested as a promising architecture with induced unnatural magnetism, especially at visible frequencies. However, it remains challenging to assemble plasmonic NPs into complex networks exhibiting strong visible magnetism. Here, a DNA‐origami‐based strategy is introduced to realize molecular self‐assembly of NPs forming complex magnetic architectures, exhibiting emergent properties including anti‐ferromagnetism, purely magnetic‐based Fano resonances, and magnetic surface plasmon polaritons. The basic building block, a gold NP (AuNP) ring consisting of six AuNP seeds, is arranged on a DNA origami frame with nanometer precision. The subsequent hierarchical assembly of the AuNP rings leads to the formation of higher‐order networks of clusters and polymeric chains. Strong emergent plasmonic properties are induced by in situ growth of silver upon the AuNP seeds. This work may facilitate the development of a tunable and scalable DNA‐based strategy for the assembly of optical magnetic circuitry, as well as plasmonic metamaterials with high fidelity.