Assembly Of Nanospheres Research Articles

Pterin-pigmented nanospheres create the colours of the polymorphic damselfly Ischnura elegans.

Animal colours commonly act as signals for mates or predators. In many damselfly species, both sexes go through a developmental colour change as adults, and females often show colour polymorphism, which may have a function in mate choice, avoidance of mating harassment and camouflage. In the blue-tailed damselfly, Ischnura elegans, young males are bright green and turn blue as they reach maturity. Females are red ( rufescens) or violet ( violacea) as immatures and, when mature, either mimic the blue colour of the males ( androchrome), or acquire an inconspicuous olive-green ( infuscans) or olive-brown ( obsoleta). The genetic basis of these differences is still unknown. Here, we quantify the colour development of all morphs of I. elegans and investigate colour formation by combining anatomical data and reflectance spectra with optical finite-difference time-domain simulations. While the coloration primarily arises from a disordered assembly of nanospheres in the epidermis, morph-dependent changes result from adjustments in the composition of pterin pigments within the nanospheres, and from associated shifts in optical density. Other pigments fine-tune hue and brilliance by absorbing stray light. These mechanisms produce an impressive palette of colours and offer guidance for genetic studies on the evolution of colour polymorphism and visual communication.

Large-Area 3D Hierarchical Superstructures Assembled from Colloidal Nanoparticles.

Assembling nanosized building blocks into macroscopic 3D complex structures is challenging. Here, nanosized metal and semiconductor building blocks with a variety of sizes and shapes (spheres, stars, and rods) are successfully assembled into a broad range of hierarchical (nanometer to micrometer) assemblies of functional materials in centimeter size using butterfly wings as templates. This is achieved by the introduction of steric hindrance to the assembly process, which compensates for attraction from the environmentally sensitive hydrogen bonds and prevents the aggregation of nanosized building blocks. Of these materials, Au nanostar assemblies show a superior enhancement in surface-enhanced Raman scattering (SERS) performance (rhodamine 6G, 1506 cm-1 ) under 532, 633, and 780 nm excitation-this is 3.1-4.4, 3.6-3.9, and 2.9-47.3 folds surpassing Au nanosphere assemblies and commercial SERS substrates (Q-SERS), respectively. This method provides a versatile route for the assembly of various nanosized building blocks into different 3D superstructures and for the construction of hybrid nanomaterials and nanocomposites.

Biomimetic Superstructures Assembled from Au Nanostars and Nanospheres for Efficient Solar Evaporation

AbstractThe control of the shapes and assembling structures of plasmonic nanoparticles is vital for the optical properties and photothermal conversion performance. Here, gold nanospheres and nanostars are assembled into ridges/disordered nanohole arrays architecture in nanoparticle colloids using light‐trapping Papilio Paris forewings (OPPs) as templates. In solar steam generation, water evaporation efficiency reaches 83.3% for nanostar assemblies (NSAs) and 68.6% for nanosphere assemblies (NSPAs) under 1‐sun (1 kW m−2) irradiation. Both the biomimetic superstructures exhibit significant enhancement of near‐infrared light absorption compared to OPPs, and NSAs show higher absorption than NSPAs in the range of 200–2500 nm. Finite element method simulations reveal such broadband absorption is ascribed to the hybridization of localized surface plasmon modes of continuous‐assembled Au nanoparticles in the biomimetic structures as well as the wing photonic structures with light‐transferring ridges with an inverted V shape and light‐trapping disordered nanohole arrays. It is revealed that optical properties of superstructures can be tuned not only by controlling their 3D structures but also by changing the shape of nanosized building blocks. It is hoped that this work will provide inspirations for the design and assembly of nanophotonic structures and devices for solar energy conversion.

Assembly of 2D graphene sheets and 3D carbon nanospheres into flexible composite electrodes for high-performance supercapacitors

Abstract Flexible paper electrodes with high conductivity and hierarchical porosity have been intensely required to develop next-generation supercapacitors with high energy density and power density. Herein, glucose-derived hydrothermal carbon nanospheres (CNSs) are chemically activated into highly porous carbon nanospheres (HPCNSs), which are uniformly dispersed by graphene oxide (GO) in water. Upon filtration, the resultant GO/HPCNS composites are assembled into a flexible composite paper of HPCNSs embedded in a parallelly arranged GO framework. Upon chemical reduction from GO to reduced graphene oxide (rGO), the rGO/HPCNS composite paper as a binder-free electrode facilitates the assembly of flexible supercapacitors. The rGO/HPCNS composite paper with optimized rGO/HPCNS ratio delivers high specific capacitance (235.3 F g −1 at 0.2 A g−1) and high cyclic stability (capacitance retention of 91% at 5 A g−1 after 5000 charge/discharge cycles), attributing to their excellent structural stability, 3D conductive network and hierarchical porosity.

Gold Nanoparticle Plasmonic Superlattices as Surface-Enhanced Raman Spectroscopy Substrates

Metal colloids are of great interest in the field of nanophotonics, mainly due to their morphology-dependent optical properties, but also because they are high-quality building blocks for complex plasmonic architectures. Close-packed colloidal supercrystals not only serve for investigating the rich plasmonic resonances arising in strongly coupled arrangements but also enable tailoring the optical response, on both the nano- and the macroscale. Bridging these vastly different length scales at reasonable fabrication costs has remained fundamentally challenging, but is essential for applications in sensing, photovoltaics or optoelectronics, among other fields. We present here a scalable approach to engineer plasmonic supercrystal arrays, based on the template-assisted assembly of gold nanospheres with topographically patterned polydimethylsiloxane molds. Regular square arrays of hexagonally packed supercrystals were achieved, reaching periodicities down to 400 nm and feature sizes around 200 nm, over areas up to 0.5 cm2. These two-dimensional supercrystals exhibit well-defined collective plasmon modes that can be tuned from the visible through the near-infrared by simple variation of the lattice parameter. We present electromagnetic modeling of the physical origin of the underlying hybrid modes and demonstrate the application of superlattice arrays as surface-enhanced Raman scattering (SERS) spectroscopy substrates which can be tailored for a specific probe laser. We therefore investigated the influence of the lattice parameter, local degree of order, and cluster architecture to identify the optimal configuration for highly efficient SERS of a nonresonant Raman probe with 785 nm excitation.

Ring-Like Assembly of Silica Nanospheres in the Presence of Amphiphilic Block Copolymer: Effects of Particle Size.

Block copolymer-mediated self-assembly of colloidal nanoparticles has attracted great attention for the fabrication of a wide variety of nanoparticle arrays. We have previously shown that silica nanospheres (SNSs) 15 nm in diameter assemble into ring-like nanostructures in the presence of amphiphilic block copolymers poly[(2-ethoxyethyl vinyl ether)- block-(2-methoxyethyl vinyl ether)] (EOVE-MOVE) in an aqueous phase. Here, the effects of particle size of SNSs on this polymer-mediated self-assembly are studied systematically using scanning electron microscopy to observe SNSs of seven different sizes between 13 to 42 nm. SNSs of 13, 16, 19, and 21 nm in diameter assemble into nanorings in the presence of EOVE-MOVE. In contrast, larger SNSs of 26, 34, and 42 nm aggregate heavily, form chain-like networks, and remain dispersed, respectively, instead of forming ring-like nanostructures. The assembly trend for 26-42 nm-SNSs agrees with that expected from the increased colloidal stability for larger particles. Time-course observation for the assembled morphology of 16 nm-SNSs reveals that the nanorings, once formed, assemble further into network-like structures, as if the nanorings behave as building units for higher-order assembly. This indicates that the ring-like assembly is a fast process that can proceed onto random colloidal aggregation. Detailed analysis of nanoring structures revealed that the average number of SNSs comprising one ring decreased from 5.0 to 3.1 with increasing the SNS size from 13 to 21 nm. A change in the number of ring members was also observed when the length of EOVE-MOVE varied while the size of SNSs was fixed. Dynamic light scattering measurements and atomic force microscopy confirmed the SNSs/polymer composite structures. We hypothesize that a stable composite morphology may exist that is influenced by both the size of SNSs and the polymer molecular structures.

Enhanced Photoelectrochemical Energy Conversion in Ultrathin Film Photoanodes with Hierarchically Tailorable Mesoscale Structure

AbstractHighly porous electrode designs are often employed for photoelectrochemical energy conversion applications. “Inverse opal” structures generate high surface area electrodes to enhance light absorption in semiconductors with short carrier collection lengths, effectively increasing the optical depth of ultrathin film photoelectrodes. Here, the fabrication of hierarchically structured, “host–guest” photoelectrodes based on selective atomic layer deposition of ZnO in composite polystyrene–SiO2 nanosphere films is described. Nanostructured scaffolds for ultrathin film photoanodes are prepared with a facile, continuously tunable solution‐phase synthesis. The characteristic length scales for absorption, carrier collection, and mass transport can be independently engineered into the electrode by choosing appropriate colloidal components for the composite scaffold. 20 nm ZnO photoanode layers based on the “host–guest” architecture exhibit roughly 500 times the photocurrent generated on an equivalent planar electrode and a 430% increase over a photoanode structured by a scaffold comprised of a close‐packed assembly of identical SiO2 nanospheres. This results from an improved balance of reactant mass transport and the locus of light absorption throughout the electrode. This approach offers a facile route for preparing strategically nanostructured photoelectrodes based on strategies developed from more complex fabrication techniques.

Microemulsion based approach for nanospheres assembly into anisotropic nanostructures of NiMnO3 and their magnetic properties

The present study focuses on synthesis of anisotropic nanostructures of nickel manganese oxide (NiMnO3) obtained by thermal decomposition of nanocrystalline nickel manganese oxalate precursor, Ni0.5Mn0.5(C2O4)·2H2O which crystallized as nanorods. The synthesis of the oxalate precursor has been carried out via microemulsion-mediated process with cationic and non-ionic surfactants. The microemulsion led to reverse micelles, and the film flexibility of the micelle in presence of non-ionic surfactant (Tergitol) was reduced by increasing the chain length of the co-surfactant (1-butanol, 1-hexanol and 1-octanol) which led to the increase in reaction rate and hence increase in the aspect ratio of the nickel manganese oxalate by up to four times. However, in the presence of cationic surfactant, highly uniform nickel manganese oxalate nanorods were obtained. Further, the decomposition of the oxalate precursor was optimized to maintain the anisotropy of the rods of ternary metal oxide (NiMnO3). An electron microscopy study showed that the rods were made up of an assembly of ultrafine nanospheres. The NiMnO3 nanostructures were all ferrimagnetic with Curie temperature ranging between 437 and 467K showing increasing saturation magnetization with increase in aspect ratio of the nanorods.

Covalent assembly of MCM-41 nanospheres on graphene oxide for improving fire retardancy and mechanical property of epoxy resin

In the study, the hierarchical nanohybrid ([email protected]) with mesoporous MCM-41 nanospheres covalent assembling on graphene oxide (GO) nanosheets was successfully prepared, aiming to improve fire retardancy of epoxy resin (EP). Fourier transformation infrared spectra (FTIR), Raman spectra, X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) verified [email protected] The nano-dispersion of [email protected] in EP was certified via TEM and XRD. Fire-retardant investigation (cone calorimeter test) revealed that EP nanocomposite with 2 wt% [email protected] possessed a 40.0% drop of peak heat release rate (pHRR) and suppressed smoke production relative to EP/GO. Intriguingly, EP/[email protected] demonstrated lower pHRR than EP/GO-MCM-41 (direct addition of GO and MCM-41). TG analysis indicated [email protected] imparted EP with significantly reduced degradation rate and increased char yield, accompanied by reduced volatile in thermogravimetric analysis couple with Fourier transformation infrared spectra (TG-FTIR) and improved aromatization in variable-temperature FTIR. The impact strength of EP/[email protected] was enhanced by 38.8% compared with EP. Contrastive analysis proposed the mechanism of neighboring synergy of GO and MCM-41, which involved in GO nanosheets wrapped by enormous carbonaceous stuffs due to MCM-41 neighboring catalysis. In perspective, hierarchical nano-assembly with neighboring synergy offered a viable approach for fire-safe polymers.

Rational Assembly of Hollow Microporous Carbon Spheres as P Hosts for Long‐Life Sodium‐Ion Batteries

AbstractThis paper reports the rational assembly of novel hollow porous carbon nanospheres (HPCNSs) as the hosts of phosphorous (P) active materials for high‐performance sodium‐ion batteries (SIBs). The vaporization‐condensation process is employed to synthesize P/C composites, which is elucidated by both theories and experiments to achieve optimized designs. The combined molecular dynamics simulations and density functional theory calculations indicate that the morphologies of polymeric P4 and the P loading in the P/C composites depend mainly on the pore size and surface condition of carbon supports. Micropores of 1–2 nm in diameter and oxygenated functional groups attached on carbon surface are essential for achieving high P loading and excellent structural stability. In light of these findings, HPCNS/amorphous red phosphorus composites with enhanced structural/functional features are synthesized, which present an extremely low volume expansion of ≈67.3% during cycles, much smaller than the commercial red P's theoretical value of ≈300%. The composite anodes deliver an exceptional sodium storage capacity and remarkable long‐life cyclic stability with capacity retention over 76% after 1000 cycles. This work signifies the importance of rational design of electrode materials based on accurate theoretical predictions and sheds light on future development of cost‐effective P/C composite anodes for commercially viable SIBs.

Self Assembly of Nickel Nanospheres into Nanoplates, Assisted by Hydrazine Hydrate

Self Assembly of Nickel Nanospheres into Nanoplates, Assisted by Hydrazine Hydrate

Magnetic properties of cube-shaped Fe3O4 nanoparticles in dilute, 2D, and 3D assemblies

The behavior of cube-shaped Fe3O4 nanoparticles is compared with that of similar spherical particles to reveal the effects of surface and shape anisotropy. Magnetostatic interactions in nanocube and nanosphere assemblies are analyzed in terms of an interaction parameter and an activation volume, and compared with theoretical predictions for the magnetic ground state of point dipole arrays with different lattice symmetries.

Facile assembly and loading of theranostic polymersomes via multi-impingement flash nanoprecipitation

Flash nanoprecipitation (FNP) has proven to be a powerful tool for the rapid and scalable assembly of solid-core nanoparticles from block copolymers. The process can be performed using a simple confined impingement jets mixer and provides an efficient and reproducible method of loading micelles with hydrophobic drugs. To date, FNP has not been applied for the fabrication of complex or vesicular nanoarchitectures capable of encapsulating hydrophilic molecules or bioactive protein therapeutics. Here, we present FNP as a single customizable method for the assembly of bicontinuous nanospheres, filomicelles and vesicular, multilamellar and tubular polymersomes from poly(ethylene glycol)-bl-poly(propylene sulfide) block copolymers. Multiple impingements of polymersomes assembled via FNP were shown to decrease vesicle diameter and polydispersity, allowing gram-scale fabrication of monodisperse polymersomes within minutes. Furthermore, we demonstrate that FNP supports the simultaneous loading of both hydrophobic and hydrophilic molecules respectively into the polymersome membrane and aqueous lumen, and encapsulated enzymes were found to be released and remain active following vesicle lysis. As an example application, theranostic polymersomes were generated via FNP that were dual loaded with the immunosuppressant rapamycin and a fluorescent dye to link targeted immune cells with the elicited immunomodulation of T cells. By expanding the capabilities of FNP, we present a rapid, scalable and reproducible method of nanofabrication for a wide range of nanoarchitectures that are typically challenging to assemble and load with therapeutics for controlled delivery and theranostic strategies.

Optical and physical properties of iridescent photonic crystals obtained by self‐assembled polymethyl methacrylate nanospheres within graphene oxide nanoplatelets

Opal photonic crystals prepared by vertical templating of polymethyl methacrylate (PMMA) nanospheres in aqueous graphene oxide (GO) solutions were successfully obtained. The results show that increasing the PMMA nanospheres' size leads to the modification of the d‐spacing in GO nanoplatelets, inducing brilliant iridescence colors that span the entire visible electromagnetic spectrum. Scanning electron microscopy study shows a uniform distribution of GO nanoplatelets on the surface and the bulk of the opal photonic crystals. The reflectance spectra exhibit a significant red shift from 385 to 660 nm when the nanospheres' size increases from 160 to 306 nm, respctively. The Raman spectra show a systematic decrease in the intensity ratio of the D to G bands of GO (ID/IG), suggesting a partial reduction of graphene oxide with decrasing the extent of defects in the partially reduced GO nanoplatelets. This finding is confirmed by the significant decrease observed in the intensity of the hydroxyl band in the attenuated total reflectance mode‐Fourier transform infrared spectra of the photonic crystals. The results provide the first demonstrated example of intercalated assemblies of polymer nanospheres within GO nanosheets, leading to photonic crystals with brilliant iridescence colors that span the entire visible electromagnetic spectrum and can be tuned only by varying the size of the PMMA nanospheres.

Assembly of methylated hollow silica nanospheres toward humidity-resistant antireflective porous films with ultralow refractive indices

Humidity-resistant antireflective (AR) porous films with ultralow refractive indices were prepared via an one-step sol–gel process by assembly of methylated hollow silica nanospheres (HSNs). The hydrophobicity and refractive indices of silica-based AR porous films could be varied between 66.0° and 115.0°, and between 1.08 and 1.14, respectively, by tuning the MTES/TEOS molar ratios. A possible assembly mechanism was proposed according to the microstructure of methylated HSNs and porous films. The various properties of silica-based AR porous films were investigated and the AR porous film could demonstrate a good AR capability of 97.6% and excellent humidity resistance.

Core–Shell Nanorod Columnar Array Combined with Gold Nanoplate–Nanosphere Assemblies Enable Powerful In Situ SERS Detection of Bacteria

Development of a label-free ultrasensitive nanosensor for detection of bacteria is presented. Sensitive assay for Gram-positive bacteria was achieved via electrostatic attraction-guided plasmonic bifacial superstructure/bacteria/columnar array assembled in one step. Dynamic optical hotspots were formed in the hybridized nanoassembly under wet-dry critical state amplifying efficiently the weak vibrational modes of three representative food-borne Gram-positive bacteria, that is, Staphylococcus xylosus, Listeria monocytogenes, and Enterococcus faecium. These three bacteria with highly analogous Raman spectra can be effectively differentiated through droplet wet-dry critical SERS approach combined with 3D PCA statistical analysis so that highly sensitive discrimination of bacterial species and samples containing mixtures of bacteria can be achieved.

Preparation and comparison of catalytic performance for nano MgFe2O4, GO-loaded MgFe2O4 and GO-coated MgFe2O4 nanocomposites

Ultrasonic-assisted and pH-dependent assembly of MgFe2O4 nanospheres and graphene oxide (GO) nanosheets, led to the formation of GO-loaded MgFe2O4 and GO-coated MgFe2O4 nanocomposites (NCs), respectively. Both of them exhibited much higher effects on the thermal decomposition of ammonium perchlorate (AP) than individual MgFe2O4. Among all the samples, GO-coated MgFe2O4 NCs exhibited the most effectively catalytic activity, which could dramatically reduce the high decomposition temperature of AP from 403.73°C to 308.68°C, enhance the energy release of AP from 649.6Jg−1 to 1526Jg−1, and decrease the apparent activation energy of AP from 138.7kJmol−1 to 116.9kJmol−1. The synergy effect between a multi-layer structure of GO nanosheets and uniformly dispersed MgFe2O4 nanospheres, as well as the strong electrostatic interactions between GO and MgFe2O4, facilitated the MgFe2O4 charge separation and transfer, thereby leading to highly efficient and robust catalytic activity.

Kinetically Controlled Assembly of Nitrogen-Doped Invaginated Carbon Nanospheres with Tunable Mesopores.

Mesoporous hollow carbon nanospheres (MHCS) have been extensively studied owning to their unique structural features and diverse potential applications. A surfactant-free self-assembly approach between resorcinol/formaldehyde and silicon alkoxide has emerged as an important strategy to prepare MHCS. Extending such a strategy to other substituted phenols to produce heterogeneous-atom-doped MHCS remains a challenge due to the very different polymerization kinetics of various resins. Herein, we report an ethylenediamine-assisted strategy to control the cooperative self-assembly between a 3-aminophenol/formaldehyde resin and silica templates. Nitrogen-doped mesoporous invaginated carbon nanospheres (N-MICS) with an N content of 6.18 at %, high specific surface areas (up to 1118 m2 g-1 ), large pore volumes (2.47 cm3 g-1 ), and tunable mesopores (3.7-11.1 nm) have been prepared. When used as electrical double-layer supercapacitors, N-MICS show a high capacitance of 261 F g-1 , an outstanding cycling stability (≈94 % capacitance retention after 10 000 cycles), and a good rate performance.

Instantaneous photoinduced patterning of an azopolymer colloidal nanosphere assembly

Colloidal azopolymer nanospheres assembled on a glass substrate were exposed to a single collimated laser beam. The combination of photo-fluidic elongation of the spherical colloids and light induced self-organization of the azopolymer film allows the quasi-instantaneous growth of a large amplitude surface relief grating. Pre-structuration of the sample with the nanosphere assembly supports faster creation of the spontaneous pattern. Confinement into the nanospheres provides exceptionally large modulation amplitude of the spontaneous relief. The method is amenable to any kind of photoactive azo-materials.

A Mesoporous Superlattice Consisting of Alternately Stacking Interstitial Nanospace within Binary Silica Colloidal Crystals

A novel class of nonclassical structures of mesoporous silica, namely a binary nanoparticle mesoporous superlattice (BNMS), is obtained by the assembly of silica nanospheres of different sizes into a binary colloidal crystal. The colloidal crystal has a CrB-type structure and consists of alternate stacks of unary fcc and binary AlB2 -type structures along the b axis and has four types of interstitial mesopores. The BNMS can be deposited on a substrate by dip coating to form an oriented thin film in which the direction of the superstructure (b axis) is perpendicular to the substrate.