Showing papers by "Younan Xia published in 2014"

Engineered Nanoparticles for Drug Delivery in Cancer Therapy

Abstract: In medicine, nanotechnology has sparked a rapidly growing interest as it promises to solve a number of issues associated with conventional therapeutic agents, including their poor water solubility (at least, for most anticancer drugs), lack of targeting capability, nonspecific distribution, systemic toxicity, and low therapeutic index. Over the past several decades, remarkable progress has been made in the development and application of engineered nanoparticles to treat cancer more effectively. For example, therapeutic agents have been integrated with nanoparticles engineered with optimal sizes, shapes, and surface properties to increase their solubility, prolong their circulation half-life, improve their biodistribution, and reduce their immunogenicity. Nanoparticles and their payloads have also been favorably delivered into tumors by taking advantage of the pathophysiological conditions, such as the enhanced permeability and retention effect, and the spatial variations in the pH value. Additionally, targeting ligands (e.g., small organic molecules, peptides, antibodies, and nucleic acids) have been added to the surface of nanoparticles to specifically target cancerous cells through selective binding to the receptors overexpressed on their surface. Furthermore, it has been demonstrated that multiple types of therapeutic drugs and/or diagnostic agents (e.g., contrast agents) could be delivered through the same carrier to enable combination therapy with a potential to overcome multidrug resistance, and real-time readout on the treatment efficacy. It is anticipated that precisely engineered nanoparticles will emerge as the next-generation platform for cancer therapy and many other biomedical applications.

Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction

Abstract: An effective strategy for reducing the Pt content while retaining the activity of a Pt-based catalyst is to deposit the Pt atoms as ultrathin skins of only a few atomic layers thick on nanoscale substrates made of another metal. During deposition, however, the Pt atoms often take an island growth mode because of a strong bonding between Pt atoms. Here we report a versatile route to the conformal deposition of Pt as uniform, ultrathin shells on Pd nanocubes in a solution phase. The introduction of the Pt precursor at a relatively slow rate and high temperature allowed the deposited Pt atoms to spread across the entire surface of a Pd nanocube to generate a uniform shell. The thickness of the Pt shell could be controlled from one to six atomic layers by varying the amount of Pt precursor added into the system. Compared to a commercial Pt/C catalyst, the Pd@PtnL (n = 1–6) core–shell nanocubes showed enhancements in specific activity and durability toward the oxygen reduction reaction (ORR). Density functiona...

Radioactive 198Au-Doped Nanostructures with Different Shapes for In Vivo Analyses of Their Biodistribution, Tumor Uptake, and Intratumoral Distribution

Abstract: With Au nanocages as an example, we recently demonstrated that radioactive 198Au could be incorporated into the crystal lattice of Au nanostructures for simple and reliable quantification of their in vivo biodistribution by measuring the γ radiation from 198Au decay and for optical imaging by detecting the Cerenkov radiation. Here we extend the capability of this strategy to synthesize radioactive 198Au nanostructures with a similar size but different shapes and then compare their biodistribution, tumor uptake, and intratumoral distribution using a murine EMT6 breast cancer model. Specifically, we investigated Au nanospheres, nanodisks, nanorods, and cubic nanocages. After PEGylation, an aqueous suspension of the radioactive Au nanostructures was injected into a tumor-bearing mouse intravenously, and their biodistribution was measured from the γ radiation while their tumor uptake was directly imaged using the Cerenkov radiation. Significantly higher tumor uptake was observed for the Au nanospheres and nan...

Stimuli-Responsive Materials for Controlled Release of Theranostic Agents

Abstract: Stimuli-responsive materials are so named because they can alter their physicochemical properties and/or structural conformations in response to specific stimuli. The stimuli can be internal, such as physiological or pathological variations in the target cells/tissues, or external, such as optical and ultrasound radiations. In recent years, these materials have gained increasing interest in biomedical applications due to their potential for spatially and temporally controlled release of theranostic agents in response to the specific stimuli. This article highlights several recent advances in the development of such materials, with a focus on their molecular designs and formulations. The future of stimuli-responsive materials will also be explored, including combination with molecular imaging probes and targeting moieties, which could enable simultaneous diagnosis and treatment of a specific disease, as well as multi-functionality and responsiveness to multiple stimuli, all important in overcoming intrinsic biological barriers and increasing clinical viability.

Emerging Applications of Phase- Change Materials ( PCMs): Teaching an Old Dog New Tricks

Abstract: The nebulous term phase-change material (PCM) simply refers to any substance that has a large heat of fusion and a sharp melting point PCMs have been used for many years in commercial applications, mainly for heat management purposes However, these fascinating materials have recently been rediscovered and applied to a broad range of technologies, such as smart drug delivery, information storage, barcoding, and detection With the hope of kindling interest in this incredibly versatile range of materials, this Review presents an array of aspects related to the compositions, preparations, and emerging applications of PCMs

Successive, Seed-Mediated Growth for the Synthesis of Single-Crystal Gold Nanospheres with Uniform Diameters Controlled in the Range of 5–150 nm

Abstract: A simple and robust route is described to the synthesis of single-crystal Au nanospheres with diameters controlled in the range of 5 nm to 150 nm. The success of this synthesis relies on the use of single-crystal Au spheres with different diameters as the seeds for successive growth and the use of a slow injection rate for the precursor to enable surface diffusion for the atoms added onto the surface of a seed. The diameters could be precisely controlled by varying the size and/or number of the seeds. The products exhibit excellent uniformity in terms of both size and shape and they are expected to find widespread use in a number of applications, including self-assembly, fabrication of metallodielectric photonic crystals, plasmonics, and biomedical research.

Oxidative Etching and Its Role in Manipulating the Nucleation and Growth of Noble-Metal Nanocrystals

Abstract: Oxidative etching plays an important role in the synthesis of metal nanocrystals. This is because the zerovalent species, including atoms, clusters, and nanocrystallites, can all be oxidized back to the ionic form and thus altering the types and distributions of products formed in both the nucleation and growth steps. In the first part of this review, we discuss the critical components needed for oxidative etching, as well as methods for enabling or preventing oxidative etching in a synthesis. We then present and analyze a number of interesting experimental observations caused by oxidative etching. In the following sections, we highlight four major applications of oxidative etching in the synthesis of metal nanocrystals, with regards to experimental controls over the crystallinity, size, shape, morphology, and growth kinetics.

Polyol Synthesis of Ultrathin Pd Nanowires via Attachment-Based Growth and Their Enhanced Activity towards Formic Acid Oxidation

Abstract: Palladium wavy nanowires with an ultrathin diameter of 2 nm are synthesized using the polyol method without the involvement of any template. The success of this synthesis relies on the use of a suitable precursor that could be reduced instantaneously to generate a large number of small Pd nanoparticles. Due to a quick depletion of precursor, the small nanoparticles were unable to grow in size through atomic addition. In the case of low surface charges and high surface energies, these small nanoparticles were forced to coalesce into ultrathin nanowires with a wavy morphology via an attachment mechanism. Thanks to the unique structure and involvement of twin defects, the as-obtained Pd ultrathin nanowires show a catalytic current density of 2.5 times higher than the conventional Pd/C catalyst towards formic acid oxidation. This work not only offers a powerful route to the synthesis of nanowires through attachment-based growth but also opens the door to the rational design and fabrication of novel metal nanostructures with enhanced properties.

Synthesis and Characterization of Pd@Pt–Ni Core–Shell Octahedra with High Activity toward Oxygen Reduction

Abstract: The oxygen reduction reaction (ORR) on the cathode of a polymer electrolyte fuel cell requires the use of a catalyst based on Pt, one of the most expensive metals on the earth. A number of strategies, including optimization of shape or facet, formation of alloys with other metals, and incorporation of a different metal into the core, have been investigated to enhance the activity of a Pt-based catalyst and thus reduce the loading of Pt. This article reports the synthesis and characterization of Pd@Pt–Ni core–shell octahedra with high activity toward ORR. The octahedra with an edge length of 8 nm were obtained by directly depositing thin, conformal shells of a Pt–Ni alloy on Pd octahedra of 6 nm in edge length. The key to the success of this synthesis is the use of an amphiphilic solvent to ensure good compatibility between the solvents typically used for the syntheses of Pd and Pt–Ni nanocrystals. The core–shell structure was confirmed by a number of techniques, including scanning transmission electron mi...

Nanoparticles with dual responses to oxidative stress and reduced pH for drug release and anti-inflammatory applications

Abstract: Oxidative stress and reduced pH are involved in many inflammatory diseases. This study describes a nanoparticle-based system that is responsive to both oxidative stress and reduced pH in an inflammatory environment to effectively release its encapsulated curcumin, an immune-modulatory agent with potent anti-inflammatory and antioxidant capabilities. Because of the presence of Forster resonance energy transfer between curcumin and the carrier, this system also allowed us to monitor the intracellular release behavior. The curcumin released upon triggering could efficiently reduce the excess oxidants produced by the lipopolysaccharide (LPS)-stimulated macrophages. The feasibility of using the curcumin-loaded nanoparticles for anti-inflammatory applications was further validated in a mouse model with ankle inflammation induced by LPS. The results of these studies demonstrate that the proposed nanoparticle system is promising for treating oxidative stress-related diseases.

Neurite Outgrowth on Electrospun Nanofibers with Uniaxial Alignment: The Effects of Fiber Density, Surface Coating, and Supporting Substrate

Abstract: Electrospun nanofibers with uniaxial alignment have recently gained its popularity as scaffolds for neural tissue engineering. Many studies have demonstrated that the nanofibers could guide the neurites to extend along the direction of alignment, resembling the native hierarchy of the nerve tissue. However, the contact cues provided by the nanofibers can be far more complicated than just guiding the neurites to extend along them. In the current study, we used dorsal root ganglia as a model system to systematically investigate the interactions between neurites and uniaxially aligned nanofibers. We demonstrated, for the first time, that the neurites could not only project along the nanofibers, but also be directed to grow along a direction perpendicular to the aligned nanofibers, depending on the following parameters: (i) the density of nanofibers, (ii) the protein deposited on the surfaces of the nanofibers, and (iii) surface properties of the substrate on which the nanofibers were supported. We also inves...

Nanofiber scaffolds with gradients in mineral content for spatial control of osteogenesis.

Abstract: Reattachment of tendon to bone has been a challenge in orthopedic surgery. The disparate mechanical properties of the two tissues make it difficult to achieve direct surgical repair of the tendon-to-bone insertion. Healing after surgical repair typically does not regenerate the natural attachment, a complex tissue that connects tendon and bone across a gradient in both mineral content and cell phenotypes. To facilitate the regeneration of the attachment, our groups have developed a nanofiber-based scaffold with a graded mineral coating to mimic the mineral composition of the native tendon-to-bone insertion. In the present work, we evaluated the ability of this scaffold to induce graded osteogenesis of adipose-derived mesenchymal stem cells (ASCs). Results from 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay and proliferating cell nuclear antigen staining indicated that cell proliferation was negatively correlated with the mineral content. In contrast, alkaline phosphatase staining, an indicator of osteogenesis, was positively correlated with the mineral content. Likewise, runt-related transcription factor 2 (an early marker of osteoblast differentiation) and osteocalcin (a late marker of osteoblast differentiation) immunostaining were both positively correlated with the mineral content. These results indicate that a gradient in mineral content on the surface of a nanofiber scaffold is capable of inducing graded differentiation of ASCs into osteoblasts for enthesis repair.

Facile Synthesis of Iridium Nanocrystals with Well-Controlled Facets Using Seed-Mediated Growth

Abstract: Iridium nanoparticles have only been reported with roughly spherical shapes and sizes of 1–5 nm, making it impossible to investigate their facet-dependent catalytic properties. Here we report for the first time a simple method based on seed-mediated growth for the facile synthesis of Ir nanocrystals with well-controlled facets. The essence of this approach is to coat an ultrathin conformal shell of Ir on a Pd seed with a well-defined shape at a relatively high temperature to ensure fast surface diffusion. In this way, the facets on the initial Pd seed are faithfully replicated in the resultant Pd@Ir core–shell nanocrystal. With 6 nm Pd cubes and octahedra encased by {100} and {111} facets, respectively, as the seeds, we have successfully generated Pd@Ir cubes and octahedra covered by Ir{100} and Ir{111} facets. The Pd@Ir cubes showed higher H2 selectivity (31.8% vs 8.9%) toward the decomposition of hydrazine compared with Pd@Ir octahedra with roughly the same size.

Pd–Cu Bimetallic Tripods: A Mechanistic Understanding of the Synthesis and Their Enhanced Electrocatalytic Activity for Formic Acid Oxidation

Abstract: This article reports a facile synthesis of Pd-Cu bimetallic tripods with a purity over 90%. Two requirements must be met in order to form tripods: i) formation of triangular, plate-like seeds during the nucleation step and ii) preferential deposition of atoms onto the three corners of a seed during the growth step. In this synthesis, these requirements are fulfilled by adding CuCl2 and KBr into an aqueous synthesis. Specifically, it is demonstrated that the Cu atoms resulting from underpotential deposition could greatly reduce the energy barrier involved in the formation of triangular seeds with planar defects because of the much lower stacking fault energy (41 mJ·m−2 for Cu vs 220 mJ·m−2 for Pd). The Br− ions could strongly bind to the three {100} side faces of a triangular seed, forcing the Pd atoms to grow from the three corners of a seed to generate a tripod. When compared with commercial Pd black, the Pd-Cu tripods exhibited substantially enhanced catalytic activity toward the electro-oxidation of formic acid. This work offers a general strategy for the synthesis of nanocrystals with a tripod structure for catalytic applications.

Continuous and scalable production of well-controlled noble-metal nanocrystals in milliliter-sized droplet reactors.

Abstract: Noble-metal nanocrystals are essential to applications in a variety of areas, including catalysis, electronics, and photonics. Despite the large number of reports, there still exists a gap between academic studies and industrial applications due to the lack of ability to produce the nanocrystals in large quantities while still maintaining the good uniformity and precise controls. Because the nucleation and growth of colloidal nanocrystals are highly sensitive to experimental conditions, it is impractical to scale up their production by simply increasing the reaction volume. Here we report a new and practical approach based on milliliter-sized droplet reactors to the scalable production of nanocrystals. The droplets of 0.25 mL in volume were produced as a continuous flow in a fluidic device assembled from commercially available components. As a proof of concept, we have synthesized Pd, Au, and Pd-M (M = Au, Pt, and Ag) nanocrystals with controlled sizes, shapes, compositions, and structures on a scale of 1...

Scaling up the Production of Colloidal Nanocrystals: Should We Increase or Decrease the Reaction Volume?

Abstract: Recent progress in facet-controlled syntheses has started to produce nanocrystals with great promise as the next-generation catalysts for a variety of applications. To move from academic studies to industrial applications, however, one has to address the issue of scaling up a synthesis that has been commonly conducted in a batch format. There are two opposite approaches to scaling up the production of colloidal nanocrystals: increasing and decreasing the reaction volume. Contrary to conventional wisdom, continuous flow synthesis based on droplets is expected to provide a more practical platform for scaling up the synthesis. Here we highlight recent progress in using droplet reactors for the synthesis of colloidal noble-metal nanocrystals with controlled sizes and shapes, with an aim towards high-volume production.

Quick, Large‐Area Assembly of a Single‐Crystal Monolayer of Spherical Particles by Unidirectional Rubbing

Abstract: Rubbing a dry powder of particles in one direction between two rubbery substrates is found to be a quick and highly reproducible, yet inexpensive fabrication technique for assembling particle monolayers with perfect spatial registry on flat or curved surfaces. The optimum rubbing conditions - pressure and speed - for a single-crystal monolayer are shown to depend on particle size. Potential applications are in biosensors, photovoltaics, and light manipulators.

Polyol syntheses of palladium decahedra and icosahedra as pure samples by maneuvering the reaction kinetics with additives.

Abstract: This article reports a robust method based upon polyol reduction for the deterministic synthesis of Pd decahedra or icosahedra with tunable sizes and a purity approaching 100%. The success of such a selective synthesis relies on an ability to fine-tune the reaction kinetics through the addition of Na2SO4 and HCl for decahedra and icosahedra, respectively. In the absence of any additive, the product of a similar synthesis in diethylene glycol contained 10% decahedra and 90% icosahedra. By optimizing the amount of Na2SO4 (or HCl) added into the reaction solution, the percent of decahedra (or icosahedra) in the product could be increased up to 100%. The roles of Na2SO4 and HCl were also investigated in great detail, and two plausible mechanisms were proposed and validated through a set of experiments. In general, a faster reduction rate is needed for the synthesis of Pd decahedra when compared with what is needed for Pd icosahedra. This work not only offers a simple approach to the deterministic syntheses of Pd decahedra and icosahedra but also provides an in-depth understanding of the mechanisms involved in shape-controlled syntheses of noble-metal nanocrystals from the perspective of reaction kinetics. On the basis of the mechanistic understanding, we have also achieved successful synthesis of Pd decahedra as pure samples by adding a proper amount of NaOH into the system to speed up the reduction kinetics.

Controlling the Size and Composition of Nanosized Pt–Ni Octahedra to Optimize Their Catalytic Activities toward the Oxygen Reduction Reaction

Abstract: Electrocatalysts based on Pt–Ni alloys have received considerable interest in recent years owing to their remarkable activities toward the oxygen reduction reaction (ORR). Here, we report the synthesis of nanosized Pt–Ni octahedra with a range of controlled sizes and compositions in an effort to optimize their ORR activities. If we employed benzyl ether as a solvent for the synthesis, we could readily control the edge lengths of the Pt–Ni octahedra in the range of 6–12 nm and keep the Pt/Ni atomic ratio at around 2.4 by varying the amount of oleylamine added into the reaction system. If we adjusted the amount of Ni precursor, the atomic ratio of Pt to Ni in the Pt–Ni octahedra could be controlled in the range of 1.4–3.7 and their edge lengths were kept at 9 nm. For the catalysts with a Pt/Ni atomic ratio around 2.4, their specific ORR activities (per unit surface area) increased monotonically as the edge length increased from 6 to 12 nm. However, the mass activities (per unit mass of Pt) of these Pt–Ni octahedra showed a maximum value at an edge length of 9 nm. The specific and mass activities for the Pt–Ni octahedra with an edge length of 9 nm but different compositions both showed peak values at a Pt/Ni atomic ratio of 2.4.

Using SV119-gold nanocage conjugates to eradicate cancer stem cells through a combination of photothermal and chemo therapies.

Abstract: Cancer stem cells (CSCs) are believed to be responsible for the long-term growth of a tumor, as well as its metastasis and recurrence after conventional therapies. Here, it is demonstrated that the sigma-2 receptor is overexpressed on the surface of breast CSCs, and thus could serve as a biomarker for the purpose of targeting. Breast CSCs are targeted with Au nanocages (AuNCs) by functionalizing their surfaces with SV119, a synthetic small molecule capable of binding to the sigma-2 receptor with high specificity. The interiors of the AuNCs could also be loaded with an anticancer drug to be selectively delivered to breast CSCs and released in a controllable fashion. The results demonstrate that the SV119-AuNC conjugate can serve as a new platform to carry out photothermal and chemo therapies simultaneously, eradicating breast CSCs more effectively through a synergetic effect.

Maßgeschneiderte Nanopartikel für den Wirkstofftransport in der Krebstherapie

Abstract: Das Interesse der Medizin an der Nanotechnologie hat in kurzer Zeit stark zugenommen. Die Nanotechnologie konnte Losungen fur viele Probleme bieten, die mit herkommlichen Therapeutika einhergehen, wie etwa eine schlechte Wasserloslichkeit (zumindest was die meisten Antitumormittel angeht), fehlende Tumorspezifitat, nichtspezifische Verteilung, systemische Toxizitat und ein geringer therapeutischer Index. In den letzten Jahrzehnten wurden beachtliche Fortschritte bei der Entwicklung und Anwendung von technischen Nanopartikeln gemacht, um Krebs wirksamer zu behandeln. Zum Beispiel gelang der Einbau von Therapeutika in Nanopartikel, die hinsichtlich Grose, Form und Oberflacheneigenschaften optimiert wurden, um deren Loslichkeit zu verbessern, die Halbwertszeit im Blutkreislauf zu verlangern, ihre Bioverteilung zu verbessern und ihre Immunogenitat zu verringern. Auserdem wurden auch die pathophysiologischen Bedingungen, wie etwa die bessere Permeabilitat und der Retentionseffekt sowie die raumlichen Schwankungen des pH-Werts genutzt, um einen Transport von Nanopartikeln und ihrer Beladung zu Tumoren zu fordern. Ferner wurden tumordirigierende Liganden (z. B. kleine organische Molekule, Peptide, Antikorper und Nucleinsauren) an die Oberflache von Nanopartikeln addiert, um Krebszellen spezifisch durch selektive Bindung an oberflachenexprimierten Rezeptoren anzusteuern. Es wurde gezeigt, dass viele Arten von therapeutischen und/oder diagnostischen Substanzen (z. B. Kontrastmittel) mithilfe der gleichen Trager transportiert werden konnen, was Kombinationstherapien und ein Auslesen der Behandlungseffizienz in Echtzeit ermoglicht. Es ist davon auszugehen, dass sich passgenau hergestellte Nanopartikel als nachste Generation von Mitteln zur Krebstherapie und vielen anderen biomedizinischen Anwendungen entwickeln werden.

The mechanics of PLGA nanofiber scaffolds with biomimetic gradients in mineral for tendon-to-bone repair.

Abstract: Attachment of dissimilar materials is prone to failure due to stress concentrations that can arise their interface. A compositionally or structurally graded transition can dissipate these stress concentrations and thereby toughen an attachment. The interface between compliant tendon and stiff bone utilizes a monotonic change in hydroxylapatite mineral ("mineral") content to produce a gradient in mechanical properties and mitigate stress concentrations. Previous efforts to mimic the natural tendon-to-bone attachment have included electrospun nanofibrous polymer scaffolds with gradients in mineral. Mineralization of the nanofiber scaffolds has typically been achieved using simulated body fluid (SBF). Depending on the specific formulation of SBF, mineral morphologies ranged from densely packed small crystals to platelike crystal florets. Although this mineralization of scaffolds produced increases in modulus, the peak modulus achieved remained significantly below that of bone. Missing from these prior empirical approaches was insight into the effect of mineral morphology on scaffold mechanics and on the potential for the approach to ultimately achieve moduli approaching that of bone. Here, we applied two mineralization methods to generate scaffolds with spatial gradations in mineral content, and developed methods to quantify the stiffening effects and evaluate them in the context of theoretical bounds. We asked whether either of the mineralization methods we developed holds potential to achieve adequate stiffening of the scaffold, and tested the hypothesis that the smoother, denser mineral coating could attain more potent stiffening effects. Testing this hypothesis required development of and comparison to homogenization bounds, and development of techniques to estimate mineral volume fractions and spatial gradations in modulus. For both mineralization strategies, energy dispersive X-ray analysis demonstrated the formation of linear gradients in mineral concentration along the length of the scaffolds, and Raman spectroscopic analysis revealed that the mineral produced was hydroxylapatite. Mechanical testing showed that the stiffness gradient using the new method was significantly steeper. By analyzing the scaffolds using micromechanical modeling techniques and extrapolating from our experimental results, we present evidence that the new mineralization protocol has the potential to achieve levels of stiffness adequate to contribute to enhanced repair of tendon-to-bone attachments.

Synthesis of colloidal metal nanocrystals in droplet reactors: the pros and cons of interfacial adsorption.

Abstract: Droplet reactors have received considerable attention in recent years as an alternative route to the synthesis and potentially high-volume production of colloidal metal nanocrystals. Interfacial adsorption will immediately become an important issue to address when one seeks to translate a nanocrystal synthesis from batch reactors to droplet reactors due to the involvement of higher surface-to-volume ratios for the droplets and the fact that nanocrystals tend to be concentrated at the water–oil interface. Here we report a systematic study to compare the pros and cons of interfacial adsorption of metal nanocrystals during their synthesis in droplet reactors. On the one hand, interfacial adsorption can be used to generate nanocrystals with asymmetric shapes or structures, including one-sixth-truncated Ag octahedra and Au–Ag nanocups. On the other hand, interfacial adsorption has to be mitigated to obtain nanocrystals with uniform sizes and controlled shapes. We confirmed that Triton X-100, a nonionic surfact...

25th Anniversary Article: Galvanic Replacement: A Simple and Versatile Route to Hollow Nanostructures with Tunable and Well‐Controlled Properties

Abstract: This article provides a progress report on the use of galvanic replacement for generating complex hollow nanostructures with tunable and well-controlled properties. We begin with a brief account of the mechanistic understanding of galvanic replacement, specifically focused on its ability to engineer the properties of metal nanostructures in terms of size, composition, structure, shape, and morphology. We then discuss a number of important concepts involved in galvanic replacement, including the facet selectivity involved in the dissolution and deposition of metals, the impacts of alloying and dealloying on the structure and morphology of the final products, and methods for promoting or preventing a galvanic replacement reaction. We also illustrate how the capability of galvanic replacement can be enhanced to fabricate nanomaterials with complex structures and/or compositions by coupling with other processes such as co-reduction and the Kirkendall effect. Finally, we highlight the use of such novel metal nanostructures fabricated via galvanic replacement for applications ranging from catalysis to plasmonics and biomedical research, and conclude with remarks on prospective future directions.

Shape-controlled metal nanocrystals for catalytic applications

Abstract: The implication of shape control in nanocrystal synthesis goes far beyond aesthetic appeal. For metal nanocrystals, the shape not only determines their physicochemical properties but also their technological relevance for catalytic, plasmonic, photonic, and electronic applications. In particular, heterogeneous catalysis is a field that can benefit tremendously from the availability of metal nanocrystals with well-controlled shapes, which may serve to significantly increase reaction efficiency while decreasing material cost. This article provides a brief overview of our recent progress in generating shape-controlled nanocrystals with enhanced catalytic activity toward oxygen reduction and formic acid oxidation, two reactions that are crucial for the successful commercialization of fuel cell technology. The impact on other industrially important reactions will be discussed as well. We hope that this article provides a roadmap for further development of metal nanocrystal-based catalysts with enhanced performance through shape-controlled synthesis.

Non‐Invasive and In Situ Characterization of the Degradation of Biomaterial Scaffolds by Volumetric Photoacoustic Microscopy

Abstract: Degradation is among the most important properties of biomaterial scaffolds, which are indispensable for regenerative medicine. The currently used method relies on the measurement of mass loss across different samples and cannot track the degradation of an individual scaffold in situ. Here we report, for the first time, the use of multiscale photoacoustic microscopy to non-invasively monitor the degradation of an individual scaffold. We could observe alterations to the morphology and structure of a scaffold at high spatial resolution and deep penetration, and more significantly, quantify the degradation of an individual scaffold as a function of time, both in vitro and in vivo. In addition, the remodeling of vasculature inside a scaffold can be visualized simultaneously using a dual-wavelength scanning mode in a label-free manner. This optoacoustic method can be used to monitor the degradation of individual scaffolds, offering a new approach to non-invasively analyze and quantify biomaterial–tissue interactions in conjunction with the assessment of in vivo vascular parameters.

Simple and accurate methods for quantifying deformation, disruption, and development in biological tissues

Abstract: When mechanical factors underlie growth, development, disease or healing, they often function through local regions of tissue where deformation is highly concentrated. Current optical techniques to estimate deformation can lack precision and accuracy in such regions due to challenges in distinguishing a region of concentrated deformation from an error in displacement tracking. Here, we present a simple and general technique for improving the accuracy and precision of strain estimation and an associated technique for distinguishing a concentrated deformation from a tracking error. The strain estimation technique improves accuracy relative to other state-of-the-art algorithms by directly estimating strain fields without first estimating displacements, resulting in a very simple method and low computational cost. The technique for identifying local elevation of strain enables for the first time the successful identification of the onset and consequences of local strain concentrating features such as cracks and tears in a highly strained tissue. We apply these new techniques to demonstrate a novel hypothesis in prenatal wound healing. More generally, the analytical methods we have developed provide a simple tool for quantifying the appearance and magnitude of localized deformation from a series of digital images across a broad range of disciplines.

Dye-assisted gain of strongly confined surface plasmon polaritons in silver nanowires.

Abstract: Noble metal nanowires are excellent candidates as subwavelength optical components in miniaturized devices due to their ability to support the propagation of surface plasmon polaritons (SPPs). Nanoscale data transfer based on SPP propagation at optical frequencies has the advantage of larger bandwidths but also suffers from larger losses due to strong mode confinement. To overcome losses, SPP gain has been realized, but so far only for weakly confined SPPs in metal films and stripes. Here we report the demonstration of gain for subwavelength SPPs that were strongly confined in chemically prepared silver nanowires (mode area = λ(2)/40) using a dye-doped polymer film as the optical gain medium. Under continuous wave excitation at 514 nm, we measured a gain coefficient of 270 cm(-1) for SPPs at 633 nm, resulting in partial SPP loss compensation of 14%. This achievement for strongly confined SPPs represents a major step forward toward the realization of nanoscale plasmonic amplifiers and lasers.

Seed-mediated synthesis of gold tetrahedra in high purity and with tunable, well-controlled sizes.

Abstract: We report a facile synthesis of Au tetrahedra in high purity and with tunable, well-controlled sizes via seed-mediated growth. The success of this synthesis relies on the use of single-crystal, spherical Au nanocrystals as the seeds and manipulation of the reaction kinetics to induce an unsymmetrical growth pattern for the seeds. In particular, the dropwise addition of a precursor solution with a syringe pump, assisted by cetyltrimethylammonium chloride and bromide at appropriate concentrations, was found to be critical to the formation of Au tetrahedra in high purity. Their sizes could be readily tuned in the range of 30-60 nm by simply varying the amount of precursor added to the reaction solution. The current strategy not only enables the synthesis of Au tetrahedra with tunable and controlled sizes but also provides a facile and versatile approach to reducing the symmetry of nanocrystals made of a face-centered cubic lattice.

Aberration Corrected Electron Microscopy Study of Bimetallic Pd–Pt Nanocrystal: Core–Shell Cubic and Core–Frame Concave Structures

Abstract: Pd–Pt core–shell/frame bimetallic nanocrystal has attracted great interest in the applications of catalysis, plasmonics, and electronics. Controlling the shape, morphology, and chemistry of the outer Pt layer has been widely accepted as a critical factor to the realization of these applications. In this study, we provide a comprehensive study on the atomic structures, composition distribution, and 3D morphology of the shell layer in the bimetallic Pd–Pt nanocrystal with core–shell cubic and core–frame concave structures by using aberration-corrected high angle angular dark field–scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, and electron tomography. The structure and chemistry characteristics of the shell layer in the core–shell cubic and core–frame concave Pd–Pt nanocrystals have been investigated at the atomic scale to reveal the deposition and growth mechanism of Pt adatoms on to Pd cubic seeds under various conditions. In core–shell Pd–Pt cubic nanocrystals, the most ...