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Significant advances in colloidal synthesis made in the past two decades have enabled the preparation of high quality nanoparticles with well-controlled sizes, shapes, and compositions. It has recently been realized that such nanoparticles can be utilized as ‘artificial atoms’ for building new materials which not only combine the size- and shape-dependent properties of individual nanoparticles but also create new collective properties by taking advantage of their electromagnetic interactions. The controlled clustering of nanoparticle building blocks into defined geometric arrangements opens a new research area in materials science and as a result much interest has been paid to the creation of secondary structures of nanoparticles, either by direct solution growth or self-assembly methods. In this tutorial review, we introduce recently developed strategies for the creation and surface modification of colloidal nanoparticle clusters, demonstrate the new collective properties resulting from their secondary structures, and highlight several of their many important technological applications ranging from photonics, separation, and detection, to multimodal imaging, energy storage and transformation, and catalysis.

The interest in self‐assembly of magnetically dipolar colloids has been driven both fundamentally and practically. Colloidal dipolar spheres are interesting model systems in condensed‐matter physics as they can self‐assemble into various crystals structures that allow exploration of the phase complexity in a single sample as their interparticle interactions can be conveniently tuned within an experimentally accessible timescale. On the other hand, magnetic assembly of colloidal particles provides an effect route towards the fabrication of functional materials, particularly colloidal responsive photonic nanostructures. In this chapter, we present recent efforts towards magnetic assembly of colloidal responsive photonic nanostructures. We start with the introduction of magnetic interactions experienced by magnetic dipolar particles in suspensions. By controlling the local particle concentration and the interparticle potential, magnetic fields not only induce the self‐assembly of colloidal particles into 1D, 2D and 3D structures, but also cause the phase transitions between different structures. A magnetic field has also been considered as a convenient stimulus to tune the optical properties of photonic structures by affecting the lattice constant d, the orientation θ, or the crystal structures. Thanks to the correlation between the photonic response and the interparticle distance, we also demonstrate that the use of magnetically responsive photonic assemblies for studying fundamental problems about colloidal interactions. By taking advantage of the unique features of the magnetically responsive photonic system, we also highlight several unique practical in structural colour printing, anticounterfeiting devices, humidity sensors, and rewritable paper.

Novel nanotechnologies have allowed great improvements in the syn-thesis of catalysts with well-controlled size, shape, and surface properties. Transition metal nanostructures with specific sizes and shapes, for instance, have shown great promise as catalysts with high selectivities and relative ease of recycling. Researchers have already demonstrated new selective catalysis with solution-dispersed or supported-metal nanocatalysts, in some cases applied to new types of reactions. Several challenges remain, however, particularly in improving the structural stability of the catalytic active phase. Core-shell nanostructures are nanoparticles encapsulated and protected by an outer shell that isolates the nanoparticles and prevents their migration and coalescence during the catalytic reactions. The synthesis and characterization of effective core-shell catalysts has been at the center of our research efforts and is the focus of this Account. Efficient core-shell catalysts require porous shells that allow free access of chemical species from the outside to the surface of nanocatalysts. For this purpose, we have developed a surface-protected etching process to prepare mesoporous silica and titania shells with controllable porosity. In certain cases, we can tune catalytic reaction rates by adjusting the porosity of the outer shell. We also designed and successfully applied a silica-protected calcination method to prepare crystalline shells with high surface area, using anatase titania as a model system. We achieved a high degree of control over the crystallinity and porosity of the anatase shells, allowing for the systematic optimization of their photocatalytic activity. Core-shell nanostructures also provide a great opportunity for controlling the interaction among the different components in ways that might boost structural stability or catalytic activity. For example, we fabricated a SiO₂/Au/N-doped TiO₂ core-shell photocatalyst with a sandwich structure that showed excellent catalytic activity for the oxidation of organic compounds under UV, visible, and direct sunlight. The enhanced photocatalytic efficiency of this nanostructure resulted from an added interfacial nonmetal doping, which improved visible light absorption, and from plasmonic metal decoration that enhanced light harvesting and charge separation. In addition to our synthetic efforts, we have developed ways to evaluate the accessibility of reactants to the metal cores and to characterize the catalytic properties of the core-shell samples we have synthesized. We have adapted infrared absorption spectroscopy and titration experiments using carbon monoxide and other molecules as probes to study adsorption on the surface of metal cores in metal oxide-shell structures in situ in both gas and liquid phases. In particular, the experiments in solution have provided insights into the ease of diffusion of molecules of different sizes in and out of the shells in these catalysts.

Applied magnetic field represents an effective tool to rapidly assemble micro- and nanoscale magnetic objects into defined structures. Ordered assembly is typically achieved by using magnetic micropatterns, for which the downside is that they require advanced microfabrication techniques to produce. In addition, most conventional magnetic assembly strategies are restricted to target objects that possess magnetic properties. Herein we present a general strategy that allows convenient magnetically driven assembly of nonmagnetic objects in defined locations with high spatial resolution. The process involves immersing a polymer relief pattern in a uniformly magnetized ferrofluid, which modulates the local magnetic fields around the pattern. Nonmagnetic target objects dispersed in the same ferrofluid can then be magnetically assembled at positions defined by the polymer pattern. As the nonmagnetic polymer patterns can be conveniently fabricated at low cost through photolithography and soft-lithography processes, our method provides a general yet very effective means to assemble a wide range of nonmagnetic objects with controlled spatial distribution, paving the way toward patterning functional microstructures.

The spectroscopic and photocatalytic properties of a series of Au@TiO(2) core-shell nanostructures are characterized. The crystallinity of the TiO(2) shells was varied by changing the etching and calcination conditions. Measurements of the photoluminescence, transient absorption, and H(2) production rate permit us to look for correlations between the spectroscopic and catalytic behaviors. We found that there is a strong effect of crystallinity on the H(2) production rate and also the stretched exponential lifetime of the photoluminescence created by short-wavelength (266 and 300 nm) photoexcitation. As the TiO(2) crystallinity is increased, the photoluminescence lifetime increases from 22 to 140 ps in a 1 ns detection window, while the H(2) production rate increases by a factor of ~4. There is no discernible effect of crystallinity on the photoluminescence dynamics excited at 350 or 430 nm, or on the electronic dynamics measured by femtosecond transient absorption after excitation at 300 nm. We hypothesize that high-energy photons create reactive and emissive charge-separated states in parallel, and that both species are subject to similar electron-hole recombination processes that depend on sample crystallinity. Based on our observations, it can be concluded that the photoluminescence dynamics may be used to evaluate the potential performance of this class of photocatalysts.

Charged superparamagnetic colloidal Fe(3)O(4)@SiO(2) core-shell particles were chosen as model dipolar soft spheres to study their crystallization and magnetically induced phase transition in suspensions. The 3D colloidal crystals feature excellent magnetically responsive photonic properties with strong diffraction, fast response and wide tunability.

Recent advances in synthetic materials sciences such as the incorporation of self-assembly, sol‐gel, and layer-by-layer deposition chemistry have afforded the development of many interesting and potentially useful nanostructures. Among those, nanoarchitectures in which a core nanoparticle, often a transition metal, is encapsulated by an outer layer of a second material, typically a porous oxide, have gained much popularity recently. The shells in these so-called core‐shell nanostructures can offer a number of functionalities, including protection of the core from the outside environment, help in maintaining its compositional and structural integrity, prevention of the core from aggregating or sintering into larger particles, selective percolation of molecules in and out of the interior of the shell, increases in solubility and/or biocompatibility, and addition of new physical or chemical properties. [1‐3] More sophisticated nanostructures can also be synthesized with a void space, in a yolk‐shell or rattle-type nanoarchitecture, to create individualized nanoreactors around the core nanoparticles. [4‐6] The new properties of these nanostructures have already been exploited in sensing, [7,8] drug delivery and biomedical imaging, [9‐11] catalysis and electrocatalysis (including fuel cells), [12‐14] and the development of batteries [15] and energy storage devices. [16]

A one-step seeded growth process has been developed for the synthesis of Au nanoparticles with tunable diameters from ∼10 nm to ∼200 nm. The delicately designed growth system suppresses self-nucleation by stabilizing a concentrated growth solution with strong coordinating ligands, leading to precise size control and convenient, scalable fabrication of Au nanoparticles.

Complicated functional microparticles with complex nanostructured compartments have been synthesized from emulsion templates by lithographic compartment allocations. Our ‘top-down–bottom-up’ hybrid method will provide additional material engineering capability for the synthesis of advanced functional microparticles.

In this work we have carried out systematic studies and identified the critical role of hydrogen peroxide instead of the generally believed citrate in the well-known chemical reduction route to silver nanoplates. This improved understanding allows us to develop consistently reproducible processes for the synthesis of nanoplates with high efficiency and yields. By harnessing the oxidative power of H(2)O(2), various silver sources including silver salts and metallic silver can be directly converted to nanoplates with the assistance of an appropriate capping ligand, thus significantly enhancing the reproducibility of the synthesis. Contrary to the previous conclusion that citrate is the key component, we have determined that the group of ligands with selective adhesion to Ag (111) facets can be expanded to many di- and tricarboxylate compounds whose two nearest carboxylate groups are separated by two or three carbon atoms. We have also found that the widely used secondary ligand polyvinylpyrrolidone can be replaced by many hydroxyl group-containing compounds or even removed entirely while still producing nanoplates of excellent uniformity and stability. In addition to the general understanding of NaBH(4) as a reducing agent, it has also been found to act as a capping agent to stabilize the silver nanoparticles, prolong the initiation time required for nanoplate nucleation, and contribute to the control of the thickness as well as the aspect ratio of silver nanoplates. The improved insight into the specific roles of the reaction components and significantly enhanced reproducibility are expected to help elucidate the formation mechanism of this interesting nanostructure.

We present a general process that allows convenient production of multifunctional composite particles by direct self-assembly of hydrophobic nanoparticles on host nanostructures containing high-density surface thiol groups. Hydrophobic nanoparticles of various compositions and combinations can be directly assembled onto the host surface through the strong coordination interactions between metal cations and thiol groups. The resulting structures can be further conveniently overcoated with a layer of normal silica to stabilize the assemblies and render them highly dispersible in water for biomedical applications. As the entire fabrication process does not involve complicated surface modification procedures, the hydrophobic ligands on the nanoparticles are not disturbed significantly so that they retain their original properties such as highly efficient luminescence. Many complex composite nanostructures with tailored functions can be efficiently produced by using this versatile approach. For example, multifunctional nonspherical nanostructures can be efficiently produced by using mercapto-silica coated nano-objects of arbitrary shapes as hosts for immobilizing functional nanoparticles. Multilayer structures can also be achieved by repeating the mercapto-silica coating and nanoparticle immobilization processes. Such assembly approach will provide the research community a highly versatile, configurable, scalable, and reproducible process for the preparation of various multifunctional structures.

Mercapto-silica spheres with controllable size from ∼150 nm to ∼3.5 μm and narrow size distribution have been prepared in water using a one-pot synthesis, in which 3-mercaptopropyltrimethoxysilane (MPS) was used as the sole silica source and ammonia as the base catalyst. The hydrolysis of MPS at the early stage of the reaction produces amphiphilic silicate species which initiate the self-emulsification of the system and lead to the formation of oil-in-water emulsion droplets. Further hydrolysis and condensation promote the nucleation and growth of the mercapto-silica spheres inside the emulsion droplets. These mercapto-silica spheres are both structurally and functionally different from typical silica particles prepared from silicon alkoxides. Understanding the formation mechanism allows systematic tuning of the size of mercapto-silica spheres in a wide range by changing the amount of precursor, the concentration of ammonia, the amount of additional surfactants, and the reaction time. We find that Ostwald ripening may occur quickly if the spheres are kept in the reaction solution, resulting in significant broadening of the particle size distribution. In order to obtain uniform and stable samples, it is important to quench the growth of the mercapto-silica spheres by separating them from the original reaction mixture and then storing them in solvents that can prevent further ripening.

Rigorous electromagnetic theory has been used to optimize elastomeric phase masks for generating sub-100-nm parallel lines by means of near-field photolithography J. A. Rogers et al., Appl. Phys. Lett. 70, 2658 (1997). In the near-field region, the scattering effect is so strong that the scalar theory is no longer adequate: A bright line was found adjacent to the dark line previously predicted by the scalar theory, and the widths of both lines were found to be insensitive to the refractive index of the photoresist. The simulation results are in good agreement with experimental studies, which showed that the bright and dark lines could be used to generate trenches and lines in a positive-tone photoresist by controlling the exposure time. Our simulations also indicate that parallel lines as small as 50 nm can be generated by adjusting the parameters of the phase mask.

Mesoscopic hollow spheres of ceramic materials whose interior surfaces were functionalized by nanoscopic objects were generated by templating sol−gel precursors against three-dimensional arrays of polystyrene beads whose surfaces had been derivatized with submonolayers of the nanoscopic objects.

In this perspective, several examples of work from our laboratory are reported where colloidal or self-assembly chemistry has been used to design new catalysts with specific properties. In the first, platinum nanoparticles with well-defined shapes have been dispersed on a high-surface-area silica support in order to take advantage of the structure sensitivity exhibited by the interconversion between the cis and trans isomers of olefins. The second case involves the use of dendrimers as scaffolding structures to prepare catalysts with small platinum nanoparticles of well-defined size. Reduced sintering of metal nanoparticles on supported catalysts is accomplished in our third example via their encapsulation inside a layer of mesoporous silica deposited on top, after metal dispersion, and etched using a newly developed surface-protection process. The final project refers to the use of yolk@shell metal-oxide systems as nanoreactors for photocatalysis. In all those examples, new synthetic nanotechnology has been directed to address a specific issue in catalysis previously identified by surface-science studies.

A one-pot solution process has been devised to synthesize colloidal Bi2Te3-Te heterogeneous nanostructures (HNs) that comprise Bi2Te3 nanoplates and Te nanorods. By controlling the reaction kinetics, the reaction of TeO3(2-) and Bi(3+) in the presence of hydrazine first produces uniform Te nanorods and then grows Bi2Te3 nanoplates on the tips and surfaces of these Te nanorods, forming various shapes including "nails", "barbells", "syringes", and "accordions". The specific topological arrangement realized arises from the peculiar anisotropic reactivity of the first formed Te nanorods, whose tips are subsequently exploited to seed the heterogeneous nucleation of Bi2Te3 as enabled by the similar crystal structure and the small lattice mismatch between Te and Bi2Te3. Three important processes, heterogeneous nucleation of Bi2Te3 on the tips and/or surface of Te nanorods, homogeneous nucleation of Bi2Te3, and the direct reaction of a Bi precursor and Te nanorods to form hollow structures via the Kirkendall Effect, occur under various conditions. The manipulation of these processes provides a robust means for the fine shape control of Bi2Te3-Te HNs. It is envisioned that the tailored synthesis of Bi2Te3-Te HNs may promise unique opportunities for producing thermoelectric materials with greatly enhanced performance.

Silver nanoplates with an extremely high aspect ratio (up to over 400) and a widely tunable surface plasmon resonance (SPR) band have been successfully synthesized by combining the concepts of selective ligand adhesion and seeded growth. Citrate ligands are used as the sole surfactant to effectively block overgrowth on the basal {111} facets and only allow growth in the lateral direction. By slowing down the reaction rate using Ag-citrate complex as precursor, the thin nature of Ag nanoplates is maintained with the edge length grown up to 4 μm, which ensures the high aspect ratio and the widely tunable SPR band. We also observe a size distribution focusing effect that helps to produce uniform nanoplates as well as narrow SPR bands over a wide range, which is important in many practical applications.

We report the rapid formation of photonic crystal structures by assembly of uniform nonmagnetic colloidal particles in ferrofluids using external magnetic fields. Magnetic manipulation of nonmagnetic particles with size down to a few hundred nanometers, suitable building blocks for producing photonic crystals with band gaps located in the visible regime, has been difficult due to their weak magnetic dipole moment. Increasing the dipole moment of magnetic holes has been limited by the instability of ferrofluids toward aggregation at high concentration or under strong magnetic field. By taking advantage of the superior stability of highly surface-charged magnetite nanocrystal-based ferrofluids, in this paper we have been able to successfully assemble 185 nm nonmagnetic polymer beads into photonic crystal structures, from 1D chains to 3D assemblies as determined by the interplay of magnetic dipole force and packing force. In a strong magnetic field with large field gradient, 3D photonic crystals with high reflectance (83%) in the visible range can be rapidly produced within several minutes, making this general strategy promising for fast creation of large-area photonic crystals using nonmagnetic particles as building blocks.

Nanoparticles of transition metals, particularly noble metals, are widely used in catalysis. However, enhancing their stability during catalytic reactions has been a challenge that has limited the full use of the benefits associated with their small size. In this Feature Article, a general "encapsulation and etching" strategy for the fabrication of nanocatalyst systems is introduced in which catalyst nanoparticles are protected within porous shells. The novelty of this approach lies in the use of chemical etching to assist the creation of mesopores in a protective oxide shell to promote efficient mass transfer to encapsulated metal nanoparticles. The etching process allows for the direct transformation of dense silica coatings into porous shells so that chemical species can reach the catalyst surface to participate in reactions while the shells act as physical barriers against aggregation of the catalyst particles. By using the surface-protected etching process, both yolk-shell and core― satellite type nanoreactors are synthesized and their utilization in liquid- and gas-phase catalysis is demonstrated. The thermal and chemical stability ofthe metallic cores during catalytic reactions is also investigated, and further work is carried out to enhance recyclability via the introduction of superparamagnetic components into the nanoreactor framework.

Protein phosphorylation plays a key role in most cellular processes. Studying phosphopeptides in complex biological samples has been a great challenge due to their low abundance as well as the coexistence of excessive amounts of salts or surfactants. In this work we demonstrate a general approach for selective separation of phosphopeptides using a class of novel mesoporous nanostructured materials. TiO(2) nanocrystals are first self-assembled into submicrometer clusters containing relatively uniform mesoscale pores and then stabilized by coating with a thin layer of silica. Calcination of the materials at high temperatures connects the neighboring nanocrystals together and enhances the mechanical stability of the clusters and at the same time removes the organic surfactants and makes the TiO(2) surface fully accessible to phosphopeptides. By coating the nanocrystal clusters with a layer of silica before calcination and removing it afterward through chemical etching, we have been able to make the cluster surface hydrophilic and negatively charged, thus enhancing the water dispersibility of the clusters and eventually their accessibility to phosphopeptides. The high selectivity and capacity of these mesoporous TiO(2) clusters have been demonstrated by effectively enriching phosphopeptides from digests of phosphoprotein (alpha- or beta-casein), protein mixtures of beta-casein and bovine serum albumin, milk, and human serum samples. We also demonstrate that the self-assembly process brings the flexibility of incorporation of multiple components, such as superparamagnetic nanocrystals, to further facilitate the peptide separation.

Clusters of densely packed hydrophobic superparamagnetic gamma-Fe(2)O(3) nanocrystals have been developed as a powerful adsorbent for enrichment of peptides and proteins, with advantages such as high enrichment efficiency, fast processing, easy magnetic separation, and direct mass analysis.

We demonstrate a water-based etching strategy for converting solid silica shells into porous ones with controllable permeability. It overcomes the challenges of the alkaline-based surface-protected etching process that we previously developed for the production of porous and hollow silica nanostructures. Mild etching around the boiling point of water partially breaks the imperfectly condensed silica network and forms soluble monosilicic acid, eventually producing mesoscale pores in the silica structures. With the surface protection from poly(vinyl pyrrolidone) (PVP), it is possible to maintain the overall shape of the silica structures while at the same time to create porosity inside. By using bulky PVP molecules which only protect the near-surface region, we are able to completely remove the interior silica and produce hollow particles. Because the etching is mild and controllable, this process is particularly useful for treating small silica particles or core-shell particles with very thin silica shells for which the alkaline-based etching method has been difficult to control. We demonstrated the precise control of the permeation of the chemical species through the porous silica shells by using a model reaction which involves the etching of Ag encapsulated inside Ag@SiO(2) by a halocarbon. It is expected that the water-based surface-protected etching method can be conveniently extended to the production of various porous silica shells containing functional materials whose diffusion to outside and/or reaction with outside species can be easily controlled.

The transmetalation of functionalized organozinc iodides with Cu(OAc)2 in THF provides a new convenient method for the preparation of functionalized organozinc-copper(I) reagents FG-RCu(OAc)ZnI which ultimately undergo 1,4-addition reaction with enones to give the products in good to excellent yields.

Multifunctional Au nanoshells with tunable optical properties and fast magnetic response have been fabricated through a sequence of sol-gel, surface-protected etching, and seed-mediated growth processes. The use of a porous silica layer enhances the uniformity of nanoshell growth, the reproducibility of the synthesis, and the structural and optical stability of the products.

Core-shell structured Fe(3)O(4)/SiO(2)/TiO(2) nanocomposites with enhanced photocatalytic activity that are capable of fast magnetic separation have been successfully synthesized by combining two steps of a sol-gel process with calcination. The as-obtained core-shell structure is composed of a central magnetite core with a strong response to external fields, an interlayer of SiO(2), and an outer layer of TiO(2) nanocrystals with a tunable average size. The convenient control over the size and crystallinity of the TiO(2) nanocatalysts makes it possible to achieve higher photocatalytic efficiency than that of commercial photocatalyst Degussa P25. The photocatalytic activity increases as the thickness of the TiO(2) nanocrystal shell decreases. The presence of SiO(2) interlayer helps to enhance the photocatalytic efficiency of the TiO(2) nanocrystal shell as well as the chemical and thermal stability of Fe(3)O(4) core. In addition, the TiO(2) nanocrystals strongly adhere to the magnetic supports through covalent bonds. We demonstrate that this photocatalyst can be easily recycled by applying an external magnetic field while maintaining their photocatalytic activity during at least eighteen cycles of use.

At room temperature, glasses are known to be brittle and fracture upon deformation. Zheng et al. show that, by exposing amorphous silica nanostructures to a low-intensity electron beam, it is possible to achieve dramatic shape changes, including a superplastic elongation of 200% for nanowires., Glasses are usually shaped through the viscous flow of a liquid before its solidification, as practiced in glass blowing. At or near room temperature (RT), oxide glasses are known to be brittle and fracture upon any mechanical deformation for shape change. Here, we show that with moderate exposure to a low-intensity (10−4 per second. We show not only large homogeneous plastic strains in compression for nanoparticles but also superplastic elongations >200% in tension for nanowires (NWs). We also report the first quantitative comparison of the load-displacement responses without and with the e-beam, revealing dramatic difference in the flow stress (up to four times). This e-beam-assisted superplastic deformability near RT is useful for processing amorphous silica and other conventionally-brittle materials for their applications in nanotechnology.

We present a new method for in-situ synthesis of multiple color and shape encoded particles in microfluidic channel using single material. Material developed in this work is M-Ink whose color is magnetically tunable and lithographically fixable. By combining novel material system and special instrumentation enables generation of limitless number of codes and greatly simplify the manufacturing process of encoded particles.

We present a novel method to fabricate photonic crystal for visible light control and demonstrate high resolution patterning of multiple structural colors using a single material. The material, termed as "M-Ink", whose color is magnetically tunable and lithographically fixable, is developed. By combining novel material system and specially designed instrument, we produce patterns with arbitrary spatial arrangements of colors with single material.

Supermolecular multilayers with high levels of compositional and structural complexities have been fabricated with an example that involves formation of stable host–guest complexes from bolaamphiphiles and cyclodextrins, followed by sequential build-up of multilayered films by these complexes in combination with anionic polystyrene sulfonate polymer chains.

This Review summarizes recent developments in the field of responsive photonic crystal structures, including principles for design and fabrication and many strategies for applications, for example as optical switches or chemical and biological sensors. A number of fabrication methods are now available to realize responsive photonic structures, the majority of which rely on self-assembly processes to achieve ordering. Compared with microfabrication techniques, self-assembly approaches have lower processing costs and higher production efficiency, however, major efforts are still needed to further develop such approaches. In fact, some emerging techniques such as spin coating, magnetic assembly, and flow-induced self-assembly have already shown great promise in overcoming current challenges. When designing new systems with improved performance, it is always helpful to bear in mind the lessons learnt from natural photonic structures.

The size and shape of it: The optical properties of Ag nanoplates can be precisely tuned in a wide range through a UV-light-induced reconstruction process in which the morphology of the nanoparticles is changed from thin triangular plates to thick round plates (see picture). This unconventional "backward tuning" strategy is a practical route to stable silver nanoplates that display a wide range of plasmon wavelengths.

Polydimethylsiloxane (PDMS) rubber can be thermally decomposed in air to produce silica vapor species which can deposit on porous anodic aluminum oxide (AAO) templates to produce silica nanotubes with a smooth surface and highly controllable thickness.

We investigate the evolution of structures that result when spherical Cd nanoparticles of a few hundred nanometers in diameter react with dissolved molecular sulfur species in solution to form hollow CdS. Over a wide range of temperatures and concentrations, we find that rapid Cd diffusion through the growing CdS shell localizes the reaction front at the outermost CdS/S interface, leading to hollow particles when all the Cd is consumed. When we examine partially reacted particles, we find that this system differs significantly from others in which the nanoscale Kirkendall effect has been used to create hollow particles. In previously reported systems, partial reaction creates a hollow particle with a spherically symmetric metal core connected to the outer shell by filaments. In contrast, here we obtain a lower symmetry structure, in which the unreacted metal core and the coalesced vacancies separate into two distinct spherical caps, minimizing the metal/void interface. This pattern of void coalescence is likely to occur in situations where the metal/vacancy self-diffusivities in the core are greater than the diffusivity of the cations through the shell.

Here we proved the principle of a multiplexed affinity-based protein complex purification (MAPcP) technique that targets simultaneous extraction of multiple protein complexes with superior purity. Microspheres of various sizes and coupled with different affinity probes extract several protein complexes concurrently and specifically. After the coextraction, flow-field flow fractionation (Fl-FFF) rapidly washes the microspheres as well as separates them based on their sizes to recover the clean individual complex for downstream analysis. Demonstration of the parallel extraction of two immuno-complexes from the yeast whole cell lysate showed that MAPcP can enhance the sample purity significantly compared to the traditional centrifugation and magnetic pull-down methods used for small scale protein purification. Simultaneous isolation of multiple protein complexes can facilitate the elucidation of the functional relationship among protein complexes and improve our understanding of the biological network.

We report the synthesis of magnetically responsive hierarchical assemblies of silica colloids that can be used as recoverable supports for nanocatalysts. Each assembly is composed of a central magnetite/silica composite core and many small satellite silica spheres. The two regions are held together as a stable unit by a polymer network of poly(N-isopropylacrylamide). The central magnetite particles are superparamagnetic at room temperature with strong magnetic response to external fields, thus providing a convenient means for separating the entire assembly from the solution. The satellite silica particles provide large surface areas for loading nanocatalysts through the well-developed silane chemistry. As an example, we demonstrate the use of such magnetically responsive hierarchical assemblies as recoverable supports for Au nanocatalysts for the reduction of 4-nitrophenol with NaBH4.

A high-temperature solution-phase hydrolysis approach has been developed for the synthesis of colloidal magnetite nanocrystals with well-controlled size and size distribution, high crystallinity, and high water solubility. The synthesis was accomplished by the hydrolysis and reduction of iron(III) cations in diethylene glycol with a rapidly injected solution of sodium hydroxide at an elevated temperature. The high reaction temperature allows for control over size and size distribution and yields highly crystalline products. The superior water solubility is achieved by using a polyelectrolyte, that is, poly(acrylic acid) as the capping agent, the carboxylate groups of which partially bind to the nanocrystal surface and partially extend into the surrounding water. The direct synthesis of water-soluble nanocrystals eliminates the need for additional surface modification steps which are usually required for treating hydrophobic nanocrystals produced in nonpolar solvents through the widely recognized pyrolysis route. The abundant carboxylate groups on the nanocrystal surface allow further modifications, such as bioconjugation, as demonstrated by linking cysteamine to the particle surface. The monodisperse, highly water-soluble, superparamagnetic, and biocompatible magnetite nanocrystals should find immediate important biomedical applications.