The capacity to respond or adapt to environmental changes is an intrinsic property of living systems that comprise highly-connected subcomponents communicating through chemical networks. The ...development of responsive synthetic systems is a relatively new research area that covers different disciplines, among which nanochemistry brings conceptually new demonstrations. Especially attractive are ligand-protected gold nanoparticles, which have been extensively used over the last decade as building blocks in constructing superlattices or dynamic aggregates, under the effect of an applied stimulus. To reflect the importance of surface chemistry and nanoparticle core composition in the dynamic self-assembly of nanoparticles, we provide here an overview of various available stimuli, as tools for synthetic chemists to exploit. Along with this task, the review starts with the use of chemical stimuli such as solvent, pH, gases, metal ions or biomolecules. It then focuses on physical stimuli: temperature, magnetic and electric fields, as well as light. To reflect on the increasing complexity of current architectures, we discuss systems that are responsive to more than one stimulus, to finally encourage further research by proposing future challenges.
Ligand-protected nanoparticles can serve as attractive building blocks for constructing complex chemical systems.
Metal colloids are of great interest in the field of nanophotonics, mainly due to their morphology-dependent optical properties, but also because they are high-quality building blocks for complex ...plasmonic architectures. Close-packed colloidal supercrystals not only serve for investigating the rich plasmonic resonances arising in strongly coupled arrangements but also enable tailoring the optical response, on both the nano- and the macroscale. Bridging these vastly different length scales at reasonable fabrication costs has remained fundamentally challenging, but is essential for applications in sensing, photovoltaics or optoelectronics, among other fields. We present here a scalable approach to engineer plasmonic supercrystal arrays, based on the template-assisted assembly of gold nanospheres with topographically patterned polydimethylsiloxane molds. Regular square arrays of hexagonally packed supercrystals were achieved, reaching periodicities down to 400 nm and feature sizes around 200 nm, over areas up to 0.5 cm2. These two-dimensional supercrystals exhibit well-defined collective plasmon modes that can be tuned from the visible through the near-infrared by simple variation of the lattice parameter. We present electromagnetic modeling of the physical origin of the underlying hybrid modes and demonstrate the application of superlattice arrays as surface-enhanced Raman scattering (SERS) spectroscopy substrates which can be tailored for a specific probe laser. We therefore investigated the influence of the lattice parameter, local degree of order, and cluster architecture to identify the optimal configuration for highly efficient SERS of a nonresonant Raman probe with 785 nm excitation.
Conspectus The primary function of the cell membrane is to protect cells from their surroundings. This entails a strict regulation on controlling the exchange of matter between the cell and its ...environment. A key factor when considering potential biological applications of a particular chemical structure has to do with its ability to internalize into cells. Molecules that can readily cross cell membranes are frequently needed in biological research and medicine, since most therapeutic entities are designed to modulate intracellular components. However, the design of molecules that do not penetrate cells is also relevant toward, for example, extracellular contrast agents, which are most widely used in clinical diagnosis. Small molecules have occupied the forefront of biomedical research until recently, but the past few decades have seen an increasing use of larger chemical structures, such as proteins or nanoparticles, leading to unprecedented and often unexpectedly novel research. Great achievements have been made toward understanding the rules that govern cellular uptake, which show that cell internalization of molecules is largely affected by their size. For example, macromolecules such as proteins and nucleic acids are usually unable to internalize cells. Intriguingly, in the case of nanoparticles, larger sizes seem to facilitate internalization via endocytic pathways, through which the particles remain trapped in lysosomes and endosomes. In this Account, we aimed at presenting our personal view of how different chemical structures behave in terms of cell internalization due to their size, ranging from small drugs to large nanoparticles. We first introduce the properties of cell membranes and the main mechanisms involved in cellular uptake. We then discuss the cellular internalization of molecules, distinguishing between those with molecular weights below 1 kDa and biological macromolecules such as proteins and nucleic acids. In the last section, we review the biological behavior of nanoparticles, with a special emphasis on plasmonic nanoparticles, which feature a high potential in the biomedical field. For each group of chemical structures, we discuss the parameters affecting their cellular internalization but also strategies that can be applied to achieve the desired intracellular delivery. Particular attention is paid to approaches that allow conditional regulation of the cell internalization process using external triggers, such as activable cell penetrating peptides, due to the impact that these systems may have in drug delivery and sensing applications. The Account ends with a “Conclusions and Outlook” section, where general lessons and future directions toward further advancements are briefly presented.
We describe a simple and efficient methodology for the aqueous synthesis of stable, uniform, and size tunable Au@Ag core–shell nanoparticles (NPs) that are stabilized by citrate ions. The synthetic ...route is based on the stepwise Ag reduction on preformed Au NPs. The final size of the core–shell NPs and therefore their optical properties can be modulated at least from 30 to 110 nm by either tuning the Ag shell thickness or changing the size of the Au core. The optical properties of the Au@Ag core–shell NPs resemble those of pure Ag NPs of similar sizes, which was confirmed by means of Mie extinction calculations. We additionally evaluated the surface-enhanced raman scattering (SERS) enhancing properties of Au@Ag core–shell NP colloids with three different laser lines (532, 633, and 785 nm). Importantly, such core–shell NPs also exhibit a higher SERS efficiency than Ag NPs of similar size under near-infrared excitation. The results obtained here serve as a basis to select Au@Ag core–shell NPs of specific size and composition with maximum SERS efficiency at their respective excitation wavelengths for SERS-based analytical and bioimaging applications.
Oleylamine in Nanoparticle Synthesis Mourdikoudis, Stefanos; Liz-Marzán, Luis M
Chemistry of materials,
05/2013, Letnik:
25, Številka:
9
Journal Article
Recenzirano
Wet chemistry in organic solvents has proven highly efficient for the preparation of several types of metallic, metal-oxide, and semiconductor nanostructures. This Short Review focuses on the use of ...oleylamine (OAm) as a versatile reagent for the synthesis of various nanoparticle systems. We describe the ability of OAm to act as a surfactant, solvent, and reducing agent, as a function of other synthesis parameters. We also discuss the specific role of OAm either alone or in combination with other reactants, to form nanostructures using a variety of organic or inorganic compounds as precursors. In certain cases OAm can form complex compounds with the metal ions of the corresponding precursor, leading to metastable compounds that can act as secondary precursors and thus be decomposed in a controlled way to yield nanoparticles. We also point out that OAm-stabilized particles can often be dispersed in different organic solvents yielding solutions with enhanced colloidal stability over long times and the potential to find applications in a number of different fields.
Progress of thermal tumor therapies and their translation into clinical practice are limited by insufficient nanoparticle concentration to release therapeutic heating at the tumor site after systemic ...administration. Herein, the use of Janus magneto‐plasmonic nanoparticles, made of gold nanostars and iron oxide nanospheres, as efficient therapeutic nanoheaters whose on‐site delivery can be improved by magnetic targeting, is proposed. Single and combined magneto‐ and photo‐thermal heating properties of Janus nanoparticles render them as compelling heating elements, depending on the nanoparticle dose, magnetic lobe size, and milieu conditions. In cancer cells, a much more effective effect is observed for photothermia compared to magnetic hyperthermia, while combination of the two modalities into a magneto‐photothermal treatment results in a synergistic cytotoxic effect in vitro. The high potential of the Janus nanoparticles for magnetic guiding confirms them to be excellent nanostructures for in vivo magnetically enhanced photothermal therapy, leading to efficient tumor growth inhibition.
Double‐faced (Janus) gold‐iron oxide nanoparticles combine magnetic and plasmonic features as smart multifunctional platforms for theranostics nanomedicine. Herein, they are proved as efficient therapeutic nanoheaters under both magnetic hyperthermia (MHT) and photothermia (PTT) procedures. Thanks to the magnetic core, PTT can be improved on‐site upon systemic administration and magnetic guiding, leading to tumor growth inhibition.
Within the field of nanotechnology, nanoparticles are one of the most prominent and promising candidates for technological applications. Self-assembly of nanoparticles has been identified as an ...important process where the building blocks spontaneously organize into ordered structures by thermodynamic and other constraints. However, in order to successfully exploit nanoparticle self-assembly in technological applications and to ensure efficient scale-up, a high level of direction and control is required. The present review critically investigates to what extent self-assembly can be directed, enhanced, or controlled by either changing the energy or entropy landscapes, using templates or applying external fields.
Anisotropic plasmonic nanoparticles have found applications in a wide range of scientific and technological fields, including medicine, energy storage and production, ultrasensitive sensing, ...catalysis, and photonics. These colloids owe their all-around success in such different scenarios to the development of rapid, scalable, and rational synthetic schemes. Gold nanotriangles (AuNTs), geometrically termed truncated triangular bipyramids, have attracted the attention of the scientific community because of their combination of well-defined crystallography, anisotropic plasmon spatial distribution, sharp tips that favor the generation of high electric fields, atomically flat surfaces, and a wide spectral tunability within the visible and infrared ranges combined with narrow bandwidths of their plasmon resonances. In this context, we previously reported a procedure for the production of AuNTs, based on a seed-mediated approach that guarantees batch-to-batch reproducibility in both size (within 5 nm in edge-length) and extinction spectra (down to 1 nm precision). The protocol involves numerous synthetic steps, and reproducibility requires awareness and familiarity with several details, which are usually learned through practice and repetition and may not always be intuitive on the basis of standard experimental protocols. We provide herein an enhanced protocol with full details and demonstration videos, which we expect will further foster the utilization of this fascinating type of anisotropic nanomaterials by researchers who are less experienced in the preparation and handling of gold colloids.
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•We discuss the main techniques to measure temperature in sub-micrometric locations.•The pros and cons of the available nanothermometry options are pointed out.•The physical/chemical ...processes behind thermal reading are explained.•The main steps towards the application of nanothermometry are discussed.
Temperature is a basic parameter influencing the behavior of systems in physics, chemistry and biology. From living cells to microcircuits, a wide range of cases require thermometry techniques that can be applied to reduced areas, offering sub-micrometric resolution and high accuracy. Since traditional thermometers cannot be applied in such systems, alternative tools have been specifically designed to measure temperature at the nanoscale; including scanning thermal microscopy, non-contact optical techniques or various types of luminescent nanoparticles. Each option presents interesting advantages, but also limitations that need to be considered and understood. We provide here an overview of the main currently available nanothermometry tools, discussing their pros and cons toward potential applications.
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