Calixarene-encapsulated nanoparticles: self-assembly into functional nanomaterials

Calixarenes are excellent surfactants for enhancing the dispersion and self-assembly of metal nanoparticles into well-defined structures, particularly those with unit length scales in the 10-100 nm size range. Particles within these ensembles are strongly coupled, giving rise to unique collective optical or magnetic properties. The self-assembled nanostructures described in this feature article include 2D arrays of colloidal Au nanoparticles with size-dependent plasmonic responses, and sub-100 nm Co nanoparticle rings with chiral magnetic states. These nanoparticle assemblies may be further developed for applications in chemical sensing based on surface-enhanced Raman scattering (SERS) and as binary elements for nonvolatile memory, respectively.     

Plasmonic vesicles of amphiphilic gold nanocrystals: self-assembly and external-stimuli-triggered destruction

We have developed a new class of plasmonic vesicular nanostructures assembled from amphiphilic gold nanocrystals with mixed polymer brush coatings. One major finding is that the integration of gold nanocrystals (nanoparticles and nanorods) with two types of chemically distinct polymer grafts, which are analogous to block copolymers as a whole, creates a new type of hybrid building block inheriting the amphiphilicity-driven self-assembly of block copolymers to form vesicular structures and the plasmonic properties of the nanocrystals. In contrast to other vesicular structures, the disruption of the plasmonic vesicles can be triggered by stimulus mechanisms inherent to either the polymer or the nanocrystal. Recent advances in nanocrystal synthesis and controlled surface-initiated polymerization have opened a wealth of possibilities for expanding this concept to other types of nanocrystals and integrating different types of nanocrystals into multifunctional vesicles. The development of multifunctional vesicles containing stimuli-responsive polymers could enable their broader applications in biosensing, multimodality imaging, and theragnostic nanomedicine.     

Core-satellites assembly of silver nanoparticles on a single gold nanoparticle via metal ion-mediated complex

We report core-satellites (Au-Ag) coupled plasmonic nanoassemblies based on bottom-up, high-density assembly of molecular-scale silver nanoparticles on a single gold nanoparticle surface, and demonstrate direct observation and quantification of enhanced plasmon coupling (i.e., intensity amplification and apparent spectra shift) in a single particle level. We also explore metal ion sensing capability based on our coupled plasmonic core-satellites, which enabled at least 1000 times better detection limit as compared to that of a single plasmonic nanoparticle. Our results demonstrate and suggest substantial promise for the development of coupled plasmonic nanostructures for ultrasensitive detection of various biological and chemical analytes.     

Magnetic-field-induced assemblies of cobalt nanoparticles

Under the influence of a 0.05 T magnetic field, 15-nm diameter cobalt nanoparticles covered with surfactants in a colloidal solution assemble into highly constrained linear chains along the direction of the magnetic field. The magnetic-field-induced (MFI) chains become floppy after removal of the field, folding into three-dimensional (3D) coiled structures upon gentle agitation. The 3D structures are broken into smaller units with vigorous agitation. The nanoparticles redisperse into the solvent upon ultrasonic agitation. Optical microscopy and transmission electron microscopy (TEM) are used to characterize the morphologies of the nanoparticle assemblies at various stages of this reversible process. The hysteresis loops and zero-field cooled/field cooled (ZFC/FC) curves reveal the interparticle coupling in the assemblies. MFI assembly provides a powerful tool to manipulate magnetic nanoparticles.     

Noble metal nanoparticles meet molecular cages: A tale of integration and synergy

Noble metal nanoparticles attract growing interest owing to their high surface-to-volume ratio and unique optical, electric and catalytic properties. Fine-tuning these properties and broadening potential applications can be envisaged if nanoparticles are coupled to supramolecular cages that afford a highly tailorable inner environment as well as rich endo-/exo-functionalization. Due to rich chemical/physical properties of cages, integration of multiple host-guest interactions in confined cavities through endo-molecular design has been achieved. Such cages provide ideal confined templates for size-controlled synthesis of ultrafine nanoparticles with superior catalytic activities. Moreover, exo-functionalization of cages offers huge opportunities to couple with nanoparticles, generating cage-nanoparticle hybrids or hierarchical assemblies that combine merits of both. The present review provides recent advances in cage-mediated nanoparticle systems with synergistic effects and integrated functions, and demonstrates their applications in catalysis, sensing, chiral amplification, plasmonic switches, imaging and cell therapy. Finally, we highlight key challenges and identify emerging directions in the coming years.     

Polyrotaxane‐Mediated Self‐Assembly of Gold Nanospheres into Fully Reversible Supercrystals

The use of a thiol‐functionalized nonionic surfactant to stabilize spherical gold nanoparticles in water induces the spontaneous formation of polyrotaxanes at the nanoparticle surface in the presence of the macrocycle α‐cyclodextrin. Whereas using an excess of surfactant an amorphous gold nanocomposite is obtained, under controlled drying conditions the self‐assembly between the surface supramolecules provides large and homogenous supercrystals with hexagonal close packing of nanoparticles. Once formed, the self‐assembled supercrystals can be fully redispersed in water. The reversibility of the crystallization process may offer an excellent reusable material to prepare gold nanoparticle inks and optical sensors with the potential to be recovered after use.     

Nanoparticles as structural and functional units in surface-confined architectures

The nanoscale engineering of functional chemical assemblies has attracted recent research effort to provide dense information storage, miniaturized sensors, efficient energy conversion, light-harvesting, and mechanical motion. Functional nanoparticles exhibiting unique photonic, electronic and catalytic properties provide invaluable building blocks for such nanoengineered architectures. Metal nanoparticle arrays crosslinked by molecular receptor units on electrodes act as selective sensing interfaces with controlled porosity and tunable sensitivity. Photosensitizer/electron-acceptor bridged arrays of Au-nanoparticles on conductive supports act as photoelectrochemically active electrodes. Semiconductor nanoparticle composites on surfaces act as efficient light collecting systems, and nanoengineered semiconductor 'core-shell' nanocrystal assemblies reveal enhanced photoelectrochemical performance due to effective charge separation. Layered metal and semiconductor nanoparticle arrays crosslinked by nucleic acids find applications in the optical, electronic and photoelectrochemical detection of DNA. Metal and semiconductor nanoparticles assembled on DNA templates may be used to generate complex electronic circuitry. Nanoparticles incorporated in hydrogel matrices yield new composite materials with novel magnetic, optical and electronic properties.     

Synthesis of Plasmonic Group‐4 Nitride Nanocrystals by Solid‐State Metathesis

Ceramic nanoparticles that exhibit a plasmonic response are promising next‐generation photonic materials. In this contribution, a solid‐state metathesis method has been reported for the synthesis of Group 4 nitride (TiN, ZrN, and HfN) nanocrystals. A high‐temperature (1000 °C) reaction between Group 4 metal oxide (TiO₂, ZrO₂, and HfO₂) nanoparticles and magnesium nitride powder yielded nitride nanocrystals that were dispersible in water. A localized surface plasmonic resonance was observed in the near‐infrared region for TiN and in the visible region of light for ZrN and HfN nanocrystals. The frequency of the plasmon resonance was dependent on the refractive index of the solvent and the nanocrystal size.     

Emerging advances in plasmonic nanoassemblies for biosensing and cell imaging

Integrating discrete plasmonic nanoparticles into assemblies can induce plasmonic coupling that produces collective plasmonic properties, which are not available for single nanoparticles. Theoretical analysis revealed that plasmonic coupling derived from assemblies could produce stronger electromagnetic field enhancement effects. Thus, plasmonic assemblies enable better performance in plasmon-based applications,such as enhanced fluorescence and Raman effects. This makes them hold great potential...     

Self-assembly of inorganic nanoparticle vesicles and tubules driven by tethered linear block copolymers

Controllable self-assembly of nanoscale building blocks into larger specific structures provides an effective route for the fabrication of new materials with unique optical, electronic, and magnetic properties. The ability of nanoparticles (NPs) to self-assemble like molecules is opening new research frontiers in nanoscience and nanotechnology. We present a new class of amphiphilic "colloidal molecules" (ACMs) composed of inorganic NPs tethered with amphiphilic linear block copolymers (BCPs). Driven by the conformational changes of tethered BCP chains, such ACMs can self-assemble into well-defined vesicular and tubular nanostructures comprising a monolayer shell of hexagonally packed NPs in selective solvents. The morphologies and geometries of these assemblies can be controlled by the size of NPs and molecular weight of BCPs. Our approach also allows us to control the interparticle distance, thus fine-tuning the plasmonic properties of the assemblies of metal NPs. This strategy provides a general means to design new building blocks for assembling novel functional materials and devices.     

Self‐Organization of Gold Nanoparticle Assemblies with 3D Spatial Order and Their External Stimuli Responsiveness

Gold nanoparticles (AuNP) with pyridyl end‐capped polystyrenes (PS‐4VP) as “quasi‐monodentate” ligands self‐assemble into ordered PS‐4VP/AuNP nanostructures with 3D hexagonal spatial order in the dried solid state. The key for the formation of these ordered structures is the modulation of the ratio AuNP versus ligands, which proves the importance of ligand design and quantity for the preparation of novel ordered polymer/metal nanoparticle conjugates. Although the assemblies of PS‐4VP/AuNP in dispersion lack in high dimensional order, strong plasmonic interactions are observed due to close contact of AuNP. Applying temperature as an external stimulus allows the reversible distortion of plasmonic interactions within the AuNP nanocomposite structures, which can be observed directly by naked eye. The modulation of the macroscopic optical properties accompanied by this structural distortion of plasmonic interaction opens up very interesting sensoric applications.

     

Spectroscopic characterizations of molecularly linked gold nanoparticle assemblies upon thermal treatment

The understanding of surface properties of core-shell type nanoparticles is important for exploiting the unique nanostructured catalytic properties. We report herein findings of a spectroscopic investigation of the thermal treatment of such nanoparticle assemblies. We have studied assemblies of gold nanocrystals of approximately 2 nm core sizes that are capped by alkanethiolate shells and are assembled by covalent or hydrogen-bonding linkages on a substrate as a model system. The structural evolution of the nanoparticle assemblies treated at different temperatures was probed by several spectroscopic techniques, including UV-visible, Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS). The results show that the capping/linking shell molecules can be effectively removed to produce controllable surface and optical properties. The data further revealed that the thermally induced evolution of the surface plasmon resonance property of gold nanoparticles is dependent on the chemical nature of the linker molecule. The spectral evolution is discussed in terms of changes in particle size, interparticle distance, and dielectric medium properties, which has important implications for controlled preparation and thermal processing of core-shell nanostructured metal catalysts.     

Nonthermal Plasma Synthesis of Nanocrystals: Fundamentals,Applications, and Future Research Needs

Nonthermal plasma synthesis has emerged as a viable alternative to nanocrystal synthesis in the liquid phase or by other gas phase based methods. The nonequilibrium environment containing free charge carriers enables the synthesis of nanocrystals with excellent crystallinity and narrow size distributions. This paper reviews the fundamental mechanisms involved in the synthesis of nanocrystals with nonthermal plasmas. It discusses the luminescent properties of plasma-produced silicon nanocrystals and their application in devices such as light emitting diodes. The ability of plasma synthesis to generate doped nanocrystals is a particularly appealing attribute. We present boron and phosphorous doped silicon nanocrystals and review their applications as near infrared plasmonic materials. Finally, the author presents his view of some important research needs in the area of nonthermal plasma synthesis of nanocrystals.     

功能纳米材料的化学控制合成、组装、结构与性能

维度限制使得纳米材料具有独特的物理和化学性质,如何对纳米构造单元的结构进行调控,并最终将纳米效应在宏观尺度上体现是当今纳米科技面临的挑战性问题,纳米材料的化学控制合成方法学、组装、结构与性能的研究是解决上述问题的基础．这篇综述文章从四个方面,分别介绍了单分散纳米晶以及纳米管、纳米线、空心纳米微球等系列低维纳米结构在合成方法与技术、“自下而上”的组装、基于微结构的性能表征与应用探索等领域取得的研究进展,试图总结出其中的规律性,同时也展现了纳米科学与技术的魅力和广阔的发展前景．     

Chemically Organizable Nanosized Materials Preparation and Applications

We are interested in fabricating well-organized assemblies of nanosized materials with wet chemical approaches for the purpose of investigating various interfacial and mesoscopic phenomena. The paper describes how to use self-assembling techniques to prepare assemblies of colloidal nanoparticles and single walled carbon nanotubes on solid surfaces. Gold nanocolloids are taken as the model system, including preparation of functionalized nanoparticles, assembling on tailored substrates, surface reorganization, and 1D, 0D controlled assembling with the aid of scanning probe lithography. The typical work we have been doing using these elaborated nanoparticle assemblies includes, the quantitative investigations of die electromagnetic coupling of particle-particle and particle-substrate in surface enhanced Raman scattering (SERS), the single electron tunneling in nanoparticle assemblies measured with scanning probe microscopy (SPM) technique, the atomic force microscopy (AFM) lithography using the surface-confined gold nanoparticles as mask.     

Colloidal Hybrid Nanostructures: A New Type of Functional Materials

One key goal of nanocrystal research is the development of experimental methods to selectively control the composition and shape of nanocrystals over a wide range of material combinations. The ability to selectively arrange nanosized domains of metallic, semiconducting, and magnetic materials into a single hybrid nanoparticle offers an intriguing route to engineer nanomaterials with multiple functionalities or the enhanced properties of one domain. In this Review, we focus on recent strategies used to create semiconductor–metal hybrid nanoparticles, present the emergent properties of these multicomponent materials, and discuss their potential applicability in different technologies.     

Bioactivation and cell targeting of semiconductor CdSe/ZnS nanocrystals with phytochelatin-related peptides

Synthetic phytochelatin-related peptides are used as an organic coat on the surface of colloidal CdSe/ZnS semiconductor nanocrystals synthesized from hydrophobic coordinating trioctyl phosphine oxide (TOPO) solvents. The peptides are designed to bind to the nanocrystals via a C-terminal adhesive domain. This adhesive domain, composed of multiple repeats of cysteines pairs flanked by hydrophobic 3-cyclohexylalanines, is followed by a flexible hydrophilic linker domain to which various bio-affinity tags can be attached. This surface coating chemistry results in small, buffer soluble, monodisperse peptide-coated nanoparticles with high colloidal stability and ensemble photophysical properties similar to those of TOPO-coated nanocrystals. Various peptide coatings are used to modulate the nanocrystal surface properties and to bioactivate the nanoparticles. CdSe/ZnS nanocrystals coated with biotinylated peptides efficiently bind to streptavidin and are specifically targeted to GPI-anchored avidin-CD14 chimeric proteins expressed on the membranes of live HeLa cells. This peptide coating surface chemistry provides a novel approach for the production of biocompatible photoluminescent nanocrystal probes.     

Template-free parallel one-dimensional assembly of gold nanoparticles

In this work, we have identified key process parameters to generate parallel unidirectional 1D assemblies of gold nanoparticles with the assistance of organic surfactants. By controlling the surfactant population, metal particle size, and amount of solvent for dispersion, the length of nanoparticle chains and their interchain space can be further tailored. In principle, the general findings of this work can also be extended to large-scale 1D organization of other transition/noble metal nanoparticles using simple organic surfactants.     

Frequency dependence of gold nanoparticle superassembly by dielectrophoresis

Dielectrophoresis is an effective method for capturing nanoparticles and assembling them into nanostructures. The frequency of the dielectrophoretic alternating current (ac) electric field greatly influences the morphology of resultant nanoparticle assemblies. In this study, frequency regimes associated with specific gold nanoparticle assembly morphologies were identified. Gold nanoparticles suspended in water were captured by microelectrodes at different electric field frequencies onto thin silicon nitride membranes. The resultant assemblies were examined by transmission electron microscopy. For this system, the major frequency-dependent influence on morphology appears to arise not from the Clausius-Mossotti factor of the dielectrophoretic force itself, but instead from ac electroosmotic fluid flow and the influence of the electrical double layer at the electrode-solution interface. Frequency regimes of technological interest include those forming one-dimensional nanoparticle chains, microwires, combinations of microwires and nanoparticle chains suitable for nanogap electrode formation, and dense three-dimensional assemblies with very high surface area.