Calculated absorption and scattering properties of gold nanoparticles of different size, shape, and composition: applications in biological imaging and biomedicine

The selection of nanoparticles for achieving efficient contrast for biological and cell imaging applications, as well as for photothermal therapeutic applications, is based on the optical properties of the nanoparticles. We use Mie theory and discrete dipole approximation method to calculate absorption and scattering efficiencies and optical resonance wavelengths for three commonly used classes of nanoparticles: gold nanospheres, silica-gold nanoshells, and gold nanorods. The calculated spectra clearly reflect the well-known dependence of nanoparticle optical properties viz. the resonance wavelength, the extinction cross-section, and the ratio of scattering to absorption, on the nanoparticle dimensions. A systematic quantitative study of the various trends is presented. By increasing the size of gold nanospheres from 20 to 80 nm, the magnitude of extinction as well as the relative contribution of scattering to the extinction rapidly increases. Gold nanospheres in the size range commonly employed ( approximately 40 nm) show an absorption cross-section 5 orders higher than conventional absorbing dyes, while the magnitude of light scattering by 80-nm gold nanospheres is 5 orders higher than the light emission from strongly fluorescing dyes. The variation in the plasmon wavelength maximum of nanospheres, i.e., from approximately 520 to 550 nm, is however too limited to be useful for in vivo applications. Gold nanoshells are found to have optical cross-sections comparable to and even higher than the nanospheres. Additionally, their optical resonances lie favorably in the near-infrared region. The resonance wavelength can be rapidly increased by either increasing the total nanoshell size or increasing the ratio of the core-to-shell radius. The total extinction of nanoshells shows a linear dependence on their total size, however, it is independent of the core/shell radius ratio. The relative scattering contribution to the extinction can be rapidly increased by increasing the nanoshell size or decreasing the ratio of the core/shell radius. Gold nanorods show optical cross-sections comparable to nanospheres and nanoshells, however, at much smaller effective size. Their optical resonance can be linearly tuned across the near-infrared region by changing either the effective size or the aspect ratio of the nanorods. The total extinction as well as the relative scattering contribution increases rapidly with the effective size, however, they are independent of the aspect ratio. To compare the effectiveness of nanoparticles of different sizes for real biomedical applications, size-normalized optical cross-sections or per micron coefficients are calculated. Gold nanorods show per micron absorption and scattering coefficients that are an order of magnitude higher than those for nanoshells and nanospheres. While nanorods with a higher aspect ratio along with a smaller effective radius are the best photoabsorbing nanoparticles, the highest scattering contrast for imaging applications is obtained from nanorods of high aspect ratio with a larger effective radius.     

Facile synthesis of mesoporous silica nanoparticles with controlled morphologies using water–acetone media

Mesoporous silica nanoparticles with controlled morphologies including nanococoons, nanorods and nanospheres have been synthesized in water–acetone media at room temperature using cetyltrimethylammonium bromide (CTAB) as the template. The obtained nanoparticles generally show hexagonal-like mesoporous structures with average pore size ranging from 2.7 to 3.3 nm and surface area from 806 to 1055 m²/g, respectively. It was found that the changes in water-to-acetone molar ratios have a dramatic impact on the morphologies of the mesoporous silica with different surface roughness, probably due to the solvent influence on the rate of the hydrolysis of tetraethoxy silane (TEOS) and the polymerization of inorganic species. Interestingly, the morphology of the mesoporous silica products can be controlled in shape from nanococoons to nanorods to nanospheres just by decreasing the water-to-acetone molar ratio from 75 to 30 to 15, respectively. From transmission electron microscopy (TEM) images, it was observed that mesoporous parallel channels run along the short axis in some areas in the nanorods, whereas the radially arranged mesopore channels are present in the nanospheres. Additionally, hydrothermal treatment leads to rougher surfaces while retaining the morphologies and nanostructures of these mesoporous silicas.     

Surfactant-assisted shape evolution of thermally synthesized TiO2 nanocrystals and their applications to efficient photoelectrodes

TiO2 nanocrystals were synthesized via a two-phase thermal process, and the shape of the nanocrystals was controlled from nanospheres to nanorods by the ratio of two surfactants. The shape control of nanocrystals was ascribed to the selective adsorption of the two surfactants. The shape of TiO2 nanocrystals influenced the photocatalytic performances of the photoelectrodes through two compromising factors: the relative surface area and the electron transport. The photoelectrode composed of nanorods showed a slower charge recombination rate, while it showed a smaller specific surface area, compared to nanospheres. As a result, the photoelectrodes showed the optimal photocatalytic performance when the nanospheres and the nanorods were mixed.     

Synthesis of multi-spiny gold nanoparticles of controlled shape and their use as a SERS substrate for the detection of pesticide residues

Russian Chemical Bulletin - Plasmonic gold nanoparticles of different shape attract much interest due to their unique physicochemical properties. Compared to gold nanorods and gold nanospheres,...     

Shape- and size-dependent refractive index sensitivity of gold nanoparticles

Gold nanoparticles of different shapes and sizes, including nanospheres, nanocubes, nanobranches, nanorods, and nanobipyramids, were dispersed into water-glycerol mixtures of varying volume ratios to investigate the response of their surface plasmon peaks to the refractive index of the surrounding medium. The refractive index sensitivities and figures of merit were found to be dependent on both the shape and the size of the Au nanoparticles. The index sensitivities generally increase as Au nanoparticles become elongated and their apexes become sharper. Au nanospheres exhibit the smallest refractive index sensitivity of 44 nm/RIU and Au nanobranches exhibit the largest index sensitivity of 703 nm/RIU. Au nanobipyramids possess the largest figures of merit, which increase from 1.7 to 4.5 as the aspect ratio is increased from 1.5 to 4.7.     

Low-frequency relaxation modes in ferroelectric liquid crystal/gold nanoparticle dispersion: impact of nanoparticle shape

Low-frequency (1 mHz–100 Hz) dielectric relaxation modes were experimentally studied in ferroelectric liquid crystal (FLC)/gold nanoparticles (nanospheres and nanorods) dispersion. It was demonstrated that the dielectric spectra of nanodispersion are strongly influenced by the shape of nanoparticles. Using different formalisms of the impedance spectroscopy, three possible low-frequency relaxation processes were found in the dispersions and the pure FLC. Due to the electrical double layers (EDLs) near nanoparticles and the alignment layers, one can observe the relaxation of the EDL polarisation around the nanoparticles (Schwarz’s relaxation) and near the driving indium tin oxide (ITO) electrodes (electrode polarisation). The other possible relaxation process is interfacial polarisation (Maxwell–Wagner mode) in which the frequency is unaffected by the nanoparticles. It was shown that Schwarz’s relaxation frequency strongly depended on the shape and size of the nanoparticles. Moreover, dispersion of nanoparticles significantly reduced direct current conductivity of the FLC mixture.     

Influence of Size and Shape on the Photocatalytic Properties of SnO2 Nanocrystals

Tuning the functional properties of nanocrystals is an important issue in nanoscience. Here, we are able to tune the photocatalytic properties of SnO₂ nanocrystals by controlling their size and shape. A structural analysis was carried out by using X‐ray diffraction (XRD)/Rietveld and transmission electron microscopy (TEM). The results reveal that the number of oxygen‐related defects varies upon changing the size and shape of the nanocrystals, which eventually influences their photocatalytic properties. Time‐resolved spectroscopic studies of the carrier relaxation dynamics of the SnO₂ nanocrystals further confirm that the electron–hole recombination process is controlled by oxygen/defect states, which can be tuned by changing the shape and size of the materials. The degradation of dyes (90 %) in the presence of SnO₂ nanoparticles under UV light is comparable to that (88 %) in the presence of standard TiO₂ Degussa P‐25 (P25) powders. The photocatalytic activity of the nanoparticles is significantly higher than those of nanorods and nanospheres because the effective charge separation in the SnO₂ nanoparticles is controlled by defect states leading to enhanced photocatalytic properties. The size‐ and shape‐dependent photocatalytic properties of SnO₂ nanocrystals make these materials interesting candidates for photocatalytic applications.     

The intragastrointestinal fate of paclitaxel-loaded micelles: Implications on oral drug delivery

The goal of the present study is to elucidate the intragastrointestinal fate of micellar delivery systems by monitoring fluorescently labeled different micelles and the model drug paclitaxel (PTX). Both in vitro and ex vivo leakage studies showed fast PTX release in fluids while micelles remained intact, except in fed-state simulated intestinal fluid and fasted-state pig intestinal fluid, thus referring to the intact absorption of micelles and PTX leakage in the gastrointestinal tract with d-α-tocopherol polyethylene glycol 1000 succinate (TPGS) micelles showing higher stability than other micelles. All groups of micelles were absorbed intact in Caco-2 and Caco-2/HT29-MTX cell models and the absorption of TPGS micelles was found to be higher than other micelles. The transport of the micelles across Caco-2/Raji (1.6%–3.5%), Caco-2 (0.8%–1%), and Caco-2/HT29-MTX (0.58%–1%) cell monolayers further verified the absorption of micelles and their subsequent transport; however, more TPGS micelles transported across cell monolayers than other groups. Moreover, the histological examination also confirmed that micelles entered the enterocytes and were transported to basolateral tissues and TPGS showed the stronger ability of penetration than other groups. Thus, these results are succinctly presenting the absorption of intact micelles in GIT confirmed by imaging evidence with prior leakage of the drug, uptake by enterocytes and the transport of micelles that survive the digestion by enterocytes and mainly by microfold cells in material nature dependent way with TPGS showing better results than other groups. In conclusion, these results identify the mechanism by which the gastrointestinal tract processes micelles and point to the likely use of this approach in the design of micelles-based therapies.     

Surface plasmon modes of gold nanospheres, nanorods, and nanoplates in an organic solvent: phase-transfer from aqueous to organic media

We present a process for the phase-transfer of gold nanoparticles from an aqueous to an organic medium with normal alkanethiols. This method can be applied not only to large nanospheres (d~100 nm) but also to anisotropic nanoparticles like nanorods and nanoplates. It allows the comparison of the nanoparticle optical properties when they are dispersed in both aqueous and organic media.     

Plasmonic nanopowders for photothermal therapy of tumors

We describe a novel strategy for the fabrication of plasmonic nanopowders (dried gold nanoparticles) by using wet chemical nanoparticle synthesis, PEG-SH functionalization, and a standard freeze-drying technique. Our strategy is illustrated by successful fabrication of different plasmonic nanopowders, including gold nanorods, gold-silver nanocages, and gold nanospheres. Importantly, the dried nanoparticles can be stored for a long time under usual conditions and then can easily be dissolved in water at a desired concentration without such hard manipulations as sonication or heating. Redispersed samples maintain the plasmonic properties of parent colloids and do not form aggregates. These properties make pegylated freeze-dried gold nanoparticles attractive candidates for plasmonic photothermal therapy in clinical settings. In this work, redispersed gold nanorods were intravenously administered to mice bearing Ehrlich carcinoma tumors at doses of 2 and 8 mg (Au)/kg (animal). Particle biodistribution was measured by atomic absorption spectroscopy, and tumor hyperthermia effects were studied under laser NIR irradiation. Significant tumor damage was observed only at the higher dose of the nanorods.     

光还原法制备不同形貌银纳米粒子及其形成机理

光还原法制备不同形貌银纳米粒子及其形成机理;光还原;纳米银;形成机理     

How to exploit different endocytosis pathways to allow selective delivery of anticancer drugs to cancer cells over healthy cells

It was recently shown that it is possible to exploit the nanoparticle shape to selectively target endocytosis pathways found in cancer and not healthy cells. It is important to understand and compare the endocytosis pathways of nanoparticles in both cancer and healthy cells to restrict the healthy cells from taking up anticancer drugs to help reduce the side effects for patients. Here, the clathrin-mediated endocytosis inhibitor, hydroxychloroquine, and the anticancer drug, doxorubicin, are loaded into the same mesoporous silica nanorods. The use of nanorods was found to restrict the uptake by healthy cells but allowed cancer cells to take up the nanorods via the macropinocytosis pathway. Furthermore, it is shown that the nanorods can selectively deliver doxorubicin to the nucleus of breast cancer cells and to the cytoplasm of pancreatic cancer cells. The dual-drug-loaded nanorods were able to selectively kill the breast cancer cells in the presence of healthy breast cells. This study opens exciting possibilities of targeting cancer cells based on the material shape rather than targeting antibodies.

It was recently shown that it is possible to exploit the nanoparticle shape to selectively target endocytosis pathways found in cancer and not healthy cells.     

Deposition of CTAB-terminated nanorods on bacteria to form highly conducting hybrid systems

Gold nanorods and nanospheres capped with positively charged CTAB are deposited on the surface of gram-positive bacterium having negatively charged teichoic acid brushes. The deposition rate is more than an order of magnitude faster than that for peptide and nucleic acid capped nanoparticles. For the nanorods, never been reported before, the strong electrostatic attraction causes the rods to bend conformally over the curved bacterium surface in random orientations. This leads to formation of an efficient percolating cluster (i.e., low contact resistance and high radius of gyration) with 104-fold higher current at 3-fold lower coverage compared to a monolayer from nanospheres. The high monolayer conductivity at only approximately 10% coverage for nanorods has potential for fabricating a novel class of bioelectronic devices by coupling electronic "nanocircuitry" at the surface to the biological function of microorganisms.     

Controlled synthesis of monodisperse sub-100 nm hollow SnO2 nanospheres: a template- and surfactant-free solution-phase route, the growth mechanism, optical properties, and application as a photocatalyst

Controlled synthesis of low‐dimensional materials, such as nanoparticles, nanorods, and hollow nanospheres, is vitally important for achieving desired properties and fabricating functional devices. We report a systematic investigation of the growth of low‐dimensional sub‐100 nm SnO₂ hollow nanostructures by a mild template‐ and surfactant‐free hydrothermal route, aiming to achieve precise control of morphology and size. The starting materials are potassium stannate and urea in an ethylene glycol (EG)/H₂O system. We found the size of the SnO₂ hollow nanospheres can be controlled by simply adjusting the urea concentration. Investigation of the mechanism of formation of the SnO₂ hollow nanospheres revealed that reaction time, urea concentration, and reaction temperature make significant contributions to the growth of hollow nanospheres. On switching the solvent from EG/H₂O to H₂O or ethanol, the SnO₂ nanostructures changed from nanospheres to ultrafine nanorods and nanoparticles. On the basis of reaction parameter dependent experiments, oriented self‐assembly and subsequent evacuation through Ostwald ripening are proposed to explain the formation of hollow nanostructures. Their size‐dependent optical properties, including UV/Vis absorption spectra and room‐temperature fluorescence spectra, were also studied. Moreover, the studies on the photocatalytic property demonstrate that the fabricated hollow structures have slightly enhanced photocatalytic degradation activity for rhodamine B when exposed to mercury light irradiation compared to solid SnO₂ nanospheres under the same conditions. The synthesized tin oxide nanoparticles display high photocatalytic efficiency and have potential applications for cleaning polluted water in the textile industry.     

Morphology-dependent voltage sensitivity of a gold nanostructure

Gold nanostructures of various morphologies, including nanospheres, nanorods, nanoprisms, and thin films, were immobilized on ITO-coated coverslips in order to investigate the response of their scattering to potential. Shifts in the plasmon band obtained by potential-modulated spectroscopic imaging indicated that the voltage sensitivity of the gold nanostructure is dependent on its morphology, with nanospheres exhibiting the lowest sensitivity and ultrathin gold films exhibiting the highest. The effects of potential on gold nanoparticles are in qualitative agreement with Mie and Gans' theories in which the shift of the gold plasma frequency is due to the charging-discharging of the nanoparticles.     

Morphology-dependent activity of silver nanostructures towards the electro-oxidation of formaldehyde

Morphological controlled silver nanoproducts have been prepared using the polyol process through varying the concentration of Na₂S. The relationship between the shape of Ag nanocatalyst and the activity for electro-oxidation of formaldehyde has also been investigated. The Ag nanoproducts were found to be efficient electrocatalysts for anodic oxidation of formaldehyde in alkaline solutions. Activity and selectivity were strongly dependent on the morphology of the silver nanoproducts. It was found that silver nanorods were more active than nanowires, nanopolyhedra and nanospheres.     

Engineered Anisotropic Fluids of Rare-Earth Nanomaterials

The self-assembly of inorganic nanoparticles into well-ordered structures in the absence of solvents is generally hindered by van der Waals forces, leading to random aggregates between them. To address the problem, we functionalized rigid rare-earth (RE) nanoparticles with a layer of flexible polymers by electrostatic complexation. Consequently, an ordered and solvent-free liquid crystal (LC) state of RE nanoparticles was realized. The RE nanomaterials including nanospheres, nanorods, nanodiscs, microprisms, and nanowires all show a typical nematic LC phase with one-dimensional orientational order, while their microstructures strongly depend on the particles’ shape and size. Interestingly, the solvent-free thermotropic LCs possess an extremely wide temperature range from −40 °C to 200 °C. The intrinsic ordering and fluidity endow anisotropic luminescence properties in the system of shearing-aligned RE LCs, offering potential applications in anisotropic optical micro-devices.     

Photothermal ablation therapy for cancer based on metal nanostructures

Besides conventional surgery, radiation therapy, and chemotherapy, which all tend to have side-effects and damage normal tissues, new medical strategies, such as photothermal sensitization and photo-thermal ablation therapy (PTA) with near-IR laser light, have been explored for treating cancer. Much of the current excitement surrounding nanoscience is directly connected to the promise of new nanotechnology for cancer diagnosis and therapy. The basic principle behind PTA is that heat generated from light can be used to destroy cancer cells. Strong optical absorption and high efficiency of photothermal conversion at the cancer sites are critical to the success of PTA. Because of their unique optical properties, e.g., strong surface plasmon resonance (SPR) absorption, noble metal nanomaterials, such as gold and silver, have been found to significantly enhance photothermal conversion for PTA applications. Substantial effort has been made to develop metal nanostructures with optimal structural and photothermal properties. Ideal metal nanostructures should have strong and tunable SPR, be easy to deliver, have low toxicity, and be convenient for bioconjugation for actively targeting specific cancer cells. This review would highlight some gold nanostructures with various shapes and properties, including nanoparticles (NPs), nanorods (NRs), nanoshells, nanocages, and hollow nanospheres, which have been studied for PTA applications. Among these structures, hollow gold nanospheres (HGNs) exhibit arguably the best combined properties because of their small size (30―50 nm), spherical shape, and strong, narrow, and tunable SPR absorption.     

Local ordering of polymer-tethered nanospheres and nanorods and the stabilization of the double gyroid phase

We present results of Brownian dynamics simulations of tethered nanospheres and tethered nanorods. Immiscibility between tether and nanoparticle facilitates microphase separation into the bicontinuous, double gyroid structure (first reported by Iacovella et al. [Phys. Rev. E 75, 040801(R) (2007)] and Horsch et al. [J. Chem. Phys. 125, 184903 (2006)], respectively). We demonstrate the ability of these nanoparticles to adopt distinct, minimal energy local packings, in which nanospheres form icosahedral-like clusters and nanorods form splayed hexagonal bundles. These local structures reduce packing frustration within the nodes of the double gyroid. We argue that the ability to locally order into stable structures is key to the formation of the double gyroid phase in these systems.     

Simultaneous LC-MS/MS Determination of Danshensu and Paeoniflorin for Permeability Studies in Caco-2 Intestinal Absorption Model

A high sensitive method based on liquid chromatography tandem mass spectrometry（LC-MS/MS） was developed and validated for the study of permeability of danshensu（DS） and paeoniflorin（PF） in Caco-2 intestinal absorption model. The DS and PF were extracted from cell culture by vacuum-lyophilizing and then separated on a Zorbax Stable Bond C18 column with 0.1% acetic acid aqueous solution and methanol as mobile phase. Detection was carried out by negative electrospray ionization（ESI ） with selected reaction monitoring（SRM） mode. The apparent permeability coefficients（Papp） of DS and PF in Caco-2 cell medium were calculated and the effects of verapamil on the coefficients Papp of the two test compounds were also illustrated. The permeability of PF was much better than that of DS when the two compounds were administrated individually. Co-administration of DS and PF led to the decrease of the transport from apical side to basolateral side for both the compounds. However, the transport in the contrary direction were accelerated. It was also observed that verapamil could accelerate the transport of the test compounds from apical side to basolateral side. However, the absorption-enhanced effect of verapamil was attenuated when DS and PF were co-administrated. These observations suggest that both passive diffusion and active efflux involved in P-gp would effect the passage of DS and PF across Caco-2 cell monolayer. At the same time, the co-administration of DS and PF to an alteration of transport behavior, which suggests that the interaction must be taken into account when ‘n-in-one＇ samples were used in Caco-2 intestinal model.