Multifunctional Nanoarchitectures Research Articles

Plasmonic/magnetic nanoarchitectures: From controllable design to biosensing and bioelectronic interfaces

Controllable design of the nanocrystal-assembled plasmonic/magnetic nanoarchitectures (P/MNAs) inspires abundant methodologies to enhance light-matter interactions and control magnetic-induced effects by means of fine-tuning the morphology and ordered packing of noble metallic or magnetic building blocks. The burgeoning development of multifunctional nanoarchitectures has opened up broad range of interdisciplinary applications including biosensing, in vitro diagnostic devices, point-of-care (POC) platforms, and soft bioelectronics. By taking advantage of their customizability and efficient conjugation with capping biomolecules, various nanoarchitectures have been integrated into high-performance biosensors with remarkable sensitivity and versatility, enabling key features that combined multiplexed detection, ease-of-use and miniaturization. In this review, we provide an overview of the representative developments of nanoarchitectures that being built by plasmonic and magnetic nanoparticles over recent decades. The design principles and key mechanisms for signal amplification and quantitative sensitivity have been explored. We highlight the structure-function programmability and prospects of addressing the main limitations for conventional biosensing strategies in terms of accurate selectivity, sensitivity, throughput, and optoelectronic integration. State-of-the-art strategies to achieve affordable and field-deployable POC devices for early multiplexed detection of infectious diseases such as COVID-19 has been covered in this review. Finally, we discuss the urgent yet challenging issues in nanoarchitectures design and related biosensing application, such as large-scale fabrication and integration with portable devices, and provide perspectives and suggestions on developing smart biosensors that connecting the materials science and biomedical engineering for personal health monitoring.

Selectively designed hierarchical copper-cobalt oxysulfide nanoarchitectures for high-rate hybrid supercapacitors

Rational design of metal oxide-sulfide-based composite electrode materials with multi-functional nanoarchitectures, high electrochemical conductivity, and superior redox activity have attracted extensive attention in high-rate hybrid supercapacitors. Herein, the hierarchical binder-free copper-cobalt oxysulfide (Cu0.33Co0.67OxSy) nanoarchitectures with flower-like nanosheets and nanoplates are facilely synthesized on Ni-foam for hybrid supercapacitors using a simple and low-cost wet chemical method. The Cu0.33Co0.67OxSy-NFs demonstrated a high specific capacity of 193 mAh/cm2 (443.9 μAh/cm2) at current density of 3 mA cm− 2, with excellent cycling performance of 95 % even after 3000 charge-discharge cycles. In addition, an aqueous hybrid device was assembled using prepared Cu0.33Co0.67OxSy-NFs as positive and porous carbon as negative electrode, which demonstrated benchmark for energy storage properties. Specifically, the assembled device exhibited a high energy density of 0.33 mWh/cm2 and a power density of 2.1 mW/cm2 with high capacity retention (91 % after 5000 cycles at 20 mA cm−2). In view of practical applicability, the assembled hybrid devices can be able to power up a small wind fan for a long duration. The cost-effective single-step approach in designing high-performance cathode materials in this study provide a strategy for the design and manufacture of other ternary metal oxysulfides for high-performance energy storage devices.

From Designing and Characterizing Multifunctional Nanoarchitectures to Commercializing Zinc Sponge–Based Alkaline Batteries That Refuse to Launch Dendrites

Our team at the Naval Research Laboratory looks at rate-critical processes where events per second are required for high performance in such areas as energy storage, energy conversion, (electro)catalysis, and sensing. We then design next-generation systems built around pore–solid nanoarchitectures that seamlessly embody all of the requisite rate functions for high-performance electrochemistry: molecular mass transport, ionic/electronic/thermal conductivity, and electron-transfer kinetics. We have taken the lessons from 20 years of probing the operational and design characteristics of energy-relevant nanoarchitectures to create a zinc sponge—a stand-alone, 3D-wired anode that improves current distribution within the electrode structure during charge–discharge cycling and thwarts dendrite-formation. With this breakthrough, we can now address the family of zinc-based rechargeable alkaline batteries: nickel–3D zinc, silver–3D zinc, MnO2–3D zinc, and even rechargeable 3D zinc–air. The route taken to move from a creative concept to fabricated reality to fundamental characterization to development within a Federal laboratory to commercialization by outside companies will be discussed.

Silicon-based nanotheranostics.

With the rapid expansion of nanoscience and nanotechnology in interdisciplinary fields, multifunctional nanomaterials have attracted particular attention. Recent advances in nanotherapeutics for cancer applications provided diverse groups of synthetic particles with defined cellular and biological functions. The advance of nanotechnology significantly increased the number of possibilities for the construction of diverse biological tools. Such materials are destined to be of great importance because of the opportunity to combine the biotechnological potential of nanoparticles together with the recognition, sensitivity and modulation of cellular pathways or genes when applied to living organisms. In this mini review three main types of Si-based nanomaterials are highlighted in the area of their application for therapy and imaging: porous silicon nanoparticles (pSiNPs), mesoporous silica nanoparticles (MSNs), focusing on their nanoconstructs containing coordination compounds, and periodic mesoporous silica nanoparticles (PMONPs). Moreover, a critical discussion on the research efforts in the construction of nanotheranostics is presented.

Self-assembly of ultrathin Cu2MoS4 nanobelts for highly efficient visible light-driven degradation of methyl orange.

We demonstrate ultrathin self-assembled Cu2MoS4 nanobelts synthesized by using Cu2O as the starting sacrificial template via a hydrothermal method. The nanobelts exhibit strong light absorption over a broad wavelength spectrum, suggesting their potential application as photocatalysts. The photocatalytic activity of nanobelts is evaluated by the degradation of Methyl Orange (MO) dye under visible light irradiation. Notably, the nanobelts can completely degrade 100 mL of 15 mg mL(-1) MO in 20 minutes with excellent recycling and structural stability, suggesting their excellent photocatalytic performance. In comparison with a sheet-like sample, the high efficiency of the self-assembled Cu2MoS4 nanobelts is attributed to a high surface area and a unique band gap, agreeing with the nitrogen adsorption analysis and photoluminescence spectra. This study offers a self-assembled synthetic route to create new multifunctional nanoarchitectures composed of atomic layers, and thus may open a window for greatly extending potential applications in water pollution treatment, photocatalytic water-splitting, solar cells and other related fields.

Multicomponent nanoarchitectures for the design of optical sensing and diagnostic tools

Simultaneous integration of multifunctional properties from different components into a hybrid nanostructure with hierarchical organization is attractive to construct new materials sought for diverse useful applications. This review highlights recent advances in the fabrication of multicomponent organic-conjugated inorganic nanoarchitectures and their potential uses in optical sensing and diagnostic tools. The similarity of the particle sizes, between inorganic hybrids and biomolecules, is the reason they can integrate into new bioconjugated nanocomposites. These multifunctional properties enable such materials to function as dual diagnostic and therapeutic agents in imaging-guided therapy. Deoxyribonucleic acid (DNA)-templated replica approaches for fabricating DNA-functionalized plasmonic nanoarchitectures are discussed to show how incorporation of metal clusters onto helical DNA structures occurs. The resulting helix plasmonic assemblies response enhanced plasmonic properties and circular dichroism signals to external environments, means they can function as highly selective bioprobes. Nanocrystal superlattices are prepared by assembling the uniform colloids by guiding the external magnetic field and solvent evaporation. The highly organized superlattices with long-range ordering exhibit optical properties tuned by external stimuli and, consequently they can be useful for desirable optical sensors and photoswitchable patterns. The efforts discussed in this review are expected to present the structural diversity of promising multifunctional nanoarchitectures for the design of efficient optical sensing and diagnostic tools.

Programmed Biologically Inspired Synthetic Templating of Multifunctional Nanoarchitectures for Small‐Scale Reactions

AbstractNature has demonstrated the ability to create highly efficient reactions on small scales by using dimensional constraints and geometric advantages in unique and powerful ways. Inspired by elegant nanoscale cytoskeletal reactions, we have demonstrated a novel method for accelerating the rates of reactions by controlling spatiotemporal relationships using synthetic templating for multifunctional nanoarchitectures. In our model system we used tetrameric β‐galactosidase, split into a pair of nonreactive dimers, and organized them to have a strong affinity for microtubules. This microtubule templating increases the concentration of the dimers to a level at which they will frequently reform into active tetramers. The reactive activity of the β‐galactosidase was monitored by X‐gal, which enabled us to demonstrate a nearly 30‐fold increase in the maximum rate of reaction. We have shown that the use of biologically inspired approaches will give us the ability to control some of the essential basics in biology and medical chemistry through increasing reaction rates. These results will have applications in a wide range of fields including nanotechnology, synthetic biology, chemistry, engineering, and polymer physics.

The right kind of interior for multifunctional electrode architectures: carbon nanofoam papers with aperiodic submicrometre pore networks interconnected in 3D

Carbon nanoarchitectures are versatile platforms for advanced electrode structures in which the carbon edifice serves multiple simultaneous functions: a massively parallel 3-D current collector with an interpenetrating structural flow field that facilitates the efficient transport of electrons, ions, and molecules throughout the structure for further functionalization or high-performance electrochemical operation. We fabricate carbon nanofoam papers by infiltrating commercially available low-density carbon fiber papers with phenolic resin. The polymer-filled paper is ambiently dried and then pyrolyzed to create lightweight, mechanically flexible, and electronically conductive sheets of ultraporous carbon with an electronic conductivity characteristic of the paper support (20–200 S cm−1) rather than RF-derived carbon (typically 0.1–1 S cm−1). The resulting composites comprise nanoscopic carbon walls that are co-continuous with an aperiodic, 3-D interconnected network of mesopores (2 to 50 nm) and macropores (50 nm to 2 µm). Macropores sized at 100–300 nm have not been adequately explored in the literature and offer ample headspace to modify internal carbon walls, thereby introducing new functionality without occluding the interconnected void volume of the nanofoam. Increasing the viscosity of the polymer sol and matching the surface energetics of the carbon fibers and aqueous sol is necessary to avoid forming a standard carbon aerogel pore–solid structure, where the pores are sized in the micropore (<2 nm) and mesopore range. Carbon nanofoam papers can be scaled in x, y, and z and are device-ready electrode structures that do not require conductive additives or polymeric binders for electrode fabrication. This one class of nanofoams serves as a high-surface-area scaffold that can be segued by appropriate modification into multifunctional nanoarchitectures that improve the performance of electrochemical capacitors, lithium-ion batteries, metal–air batteries, fuel cells, and ultrafiltration.

Architectural integration of the components necessary for electrical energy storage on the nanoscale and in 3D

We describe fabrication of three-dimensional (3D) multifunctional nanoarchitectures in which the three critical components of a battery--cathode, separator/electrolyte, and anode--are internally assembled as tricontinuous nanoscopic phases. The architecture is initiated using sol-gel chemistry and processing to erect a 3D self-wired nanoparticulate scaffold of manganese oxide (>200 m(2) g(-1)) with a continuous, open, and mesoporous void volume. The integrated 3D system is generated by exhaustive coverage of the oxide network by an ultrathin, conformal layer of insulating polymer that forms via self-limiting electrodeposition of poly(phenylene oxide). The remaining interconnected void volume is then wired with RuO(2) nanowebs using subambient thermal decomposition of RuO(4). Transmission electron microscopy demonstrates that the three nanoscopic charge-transfer functional components--manganese oxide, polymer separator/cation conductor, and RuO(2)--exhibit the stratified, tricontinuous design of the phase-by-phase construction. This architecture contains all three components required for a solid-state energy storage device within a void volume sized at tens of nanometres such that nanometre-thick distances are established between the opposing electrodes. We have now demonstrated the ability to assemble multifunctional energy-storage nanoarchitectures on the nanoscale and in three dimensions.

Research Highlights

Research Highlights

Multifunctional nanoarchitectures from DNA-based ABC monomers

The ability to attach different functional moieties to a molecular building block1,2 could lead to applications in nanoelectronics3, nanophotonics4, intelligent sensing5 and drug delivery6,7. The building unit needs to be both multivalent and anisotropic, and although many anisotropic building blocks have been created1,8,9,10,11,12, these have not been universally applicable. Recently, DNA has been used to generate various nanostructures13,14,15,16,17 or hybrid systems18,19,20,21,22,23,24,25, and as a generic building block for various applications26,27,28,29,30. Here, we report the creation of anisotropic, branched and crosslinkable building blocks (ABC monomers) from which multifunctional nanoarchitectures have been assembled. In particular, we demonstrate a target-driven polymerization process in which polymers are generated only in the presence of a specific DNA molecule, leading to highly sensitive pathogen detection. Using this monomer system, we have also designed a biocompatible nanovector that delivers both drugs and tracers simultaneously. Our approach provides a general yet versatile route towards the creation of a range of multifunctional nanoarchitectures.Supplementary informationThe online version of this article (doi:10.1038/nnano.2009.93) contains supplementary material, which is available to authorized users.

Architectural Design, Interior Decoration and Three‐Dimensional Plumbing en Route to Multifunctional Nanoarchitectures

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Architectural Design, Interior Decoration, and Three-Dimensional Plumbing en Route to Multifunctional Nanoarchitectures

Ultraporous aperiodic solids, such as aerogels and ambigels, are sol-gel-derived equivalents of architectures. The walls are defined by the nanoscopic, covalently bonded solid network of the gel. The vast open, interconnected space characteristic of a building is represented by the three-dimensionally continuous nanoscopic pore network. We discuss how an architectural construct serves as a powerful metaphor that guides the chemist in the design of aerogel-like nanoarchitectures and in their physical and chemical transformation into multifunctional objects that yield high performance for rate-critical applications.

Facilitated Lithium Storage in MoS2 Overlayers Supported on Coaxial Carbon Nanotubes

The discoveries of carbon and inorganic fullerene-like nanotubes with a wide spectra of possible applications have stimulated multi- and interdisciplinary research activities. In this paper, we prepared MoS2 overlayers supported on coaxial carbon nanotubes and investigated lithium storage/release properties in relation to their structural properties. The coaxial nanoarchitecture was successfully synthesized by a designed solution-phase route in the low temperature range, which was characterized by X-ray powder diffraction (XRD), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The reversible lithium-storage behaviors involved in the nanoarchitecture were elucidated by means of various techniques including galvanostatic methods, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). A thorough investigation of the composition−structure−property relationships of the coaxial nanoarchitecture highlighted the importance of the underlying carbon nanotubes in improving the lithium storage/release properties of the MoS2 sheath through a unique synergy at the nanoscale. This work should be notably significant for the design of new multifunctional nanoarchitectures by the wet-chemistry process, applicable for energy conversion and storage of the future.