Anionic gold ions desorbed from gold nanorods and nanospheres.

The desorption and ionization of gold anions and cations from gold nanorods and nanospheres were investigated using a matrix-assisted laser desorption/ionization mass spectrometry instrument. The signal intensities of the gold anions from nanorods with a volume of 4.8 × 103 nm3 were about 28 times larger than the signal intensities of gold anions from nanospheres of similar volume. Gold cations did not show a remarkable difference depending on the nanoparticles' shapes. The unique desorption behavior of gold anions suggests their potential as reporter ions in mass spectrometry.

Gold-Silver and Gold-Palladium Alloy Nanoparticles as Mass-Probes for Immunosensing.

Silver or palladium shelled gold nanoparticles were fused into alloy nanoparticles by pulsed-laser irradiation. The alloy nanoparticles could carry antibodies on their surfaces without affecting their immune functionalities and interact selectively with antigens on a blotting membrane. Silver or palladium ions desorbed from the alloy nanoparticles as reporter ions upon the UV laser irradiation in a mass spectrometer.

Plasmon-enhanced two-photon excitation fluorescence of rhodamine 6G and an Eu-diketonate complex by a picosecond diode laser.

Two-photon excited fluorescence (TPEF) of rhodamine 6G (Rh6G) and tris(dibenzoylmethane) mono(5-aminophenanthroline) europium (Eu-TDPA) was measured using a pulsed diode laser head (<45 mW, 975 nm, 90 ps pulse width, 40 MHz). Fluorophores were cast on a glass slide modified with triangular silver nanoprisms. A photon-counting photomultiplier detected the TPEF of Rh6G on a glass substrate (1361 Hz) and on the nanoprisms (6322 Hz). On the other hand, Eu-TDPA did not exhibit TPEF on a glass substrate. TPEF was only observed when the extinction of the nanoprisms on the substrates was larger than 0.1. The nanoprisms enhanced the TPEF of these two fluorophores up to the detectable level using a low-power laser diode.

Imaging mass spectrometry of gold nanoparticles in a tissue section as an immunohistochemical staining mass probe.

For analysis of low abundance peptides in a tissue section, immunohistochemical staining through antibody-antigen interaction is a usual technique. The antibody is conjugated with a probe moiety that aids in highly sensitive detection. Gold nanoparticles, which show excellent chemical stability and variation of surface modifications, are expected to act as a sensitive mass probe to desorb gold ions (Au+ , Au2 + , Au3 + ) that are distinguishable from fragment ions from organic molecules. Here, green fluorescent proteins (GFP) in a tissue section of a transgenic zebrafish were detected by the gold mass probe conjugated with antibodies. Due to the efficient ionization and desorption of gold ions, imaging mass spectrometry of Au2 + ions indicated the distribution of gold nanoparticles stained in a tissue section, and the mass signal distribution was consistent with the area where the GFP-expressing cells were distributed. Conventional immunofluorescence techniques showed intense autofluorescence that come from intrinsic fluorophores in the tissue section. In contrast, the gold nanoparticles acted as an immunostaining mass probe that displayed significantly lower background signals.

Stepwise Preparation of Spherical Gold Nanoparticles Passivated with Cationic Amphiphiles.

Spherical gold nanoparticles with cationic surfaces were prepared in hexadecyltrimethylammonium (CTA(+)) chloride (CTAC) and CTA(+) bromide (CTAB) solutions. In a CTAC solution, ascorbic acid reduction of gold ions (AuCl4(-)) induced spontaneous nucleation of gold clusters, which resulted in the formation of small gold nanoparticles (<5 nm). In a CTAB solution, the combination of ascorbic acid and AuBr4(-) induced low spontaneous nucleation, and therefore controllable crystal growth of seed particles was possible. To obtain uniform gold nanoparticles, seed particles (<5 nm) were first prepared in a CTAC solution using NaBH4 as a reducing agent. Subsequent growth reactions of the seeds in CTAB solutions were controllable to obtain gold nanoparticles with diameters ranging from 7 to 60 nm.

In situ observation of structural transformation of gold nanorods under pulsed laser irradiation in an HVEM.

A pulsed laser light illumination system was attached to a high-voltage electron microscope (HVEM) for in situ observation of light-induced behaviors of nano objects. The wavelength λ of emitted laser pulses was 1064, 532 or 266 nm, and the pulse duration was 6-8 ns. Using this combined HVEM system, we observed the deformation behavior of gold nanorods irradiated by a pulsed laser (λ = 1064 nm) at an intensity of 310 J m(-2) pulse or higher. A single shot of pulsed laser reduced the aspect ratio of the gold nanorods from 5 to a much smaller value. The extent of the reduction increased at higher laser intensities. However, at 310 J m(-2) pulse(-1), additional pulsed shots induced limited further deformation. The mean aspect ratio approximated to 2.5 even after irradiation with 7 pulses (total fluence exceeding 2 MJ m(-2)). In situ high resolution transmission electron microscopy (HRTEM) observation revealed that deformation was accompanied by total atomic restructuring of the nanorod interiors.

PEG-silica-modified gold nanorods that retain their optical properties in tumor tissues.

Gold nanorods modified with polyethylene glycol (PEG) chains via Au-S bonds form aggregates, and their absorption spectra broaden in tumor tissues. In contrast, the gold nanorods modified here via the crosslinking of PEG chains on the silica shell on gold nanorods showed enhanced permeability and retention effects and retained the optical properties of the original gold nanorods in tumor tissues.

CW/pulsed NIR irradiation of gold nanorods: effect on transdermal protein delivery mediated by photothermal ablation.

Transdermal delivery is a useful and attractive method for drug delivery, even though the stratum corneum is a major barrier of protein translocation into the skin. To achieve protein delivery through the stratum corneum, we first cast gold nanorods, acting as a heating device in response to near-infrared light irradiation, onto the skin surface. After applying an aqueous solution of ovalbumin to the skin, the skin was irradiated by near-infrared laser light. Irradiation of the skin using a continuous-wave laser increased the skin temperature resulting in an efficient translocation of ovalbumin into the skin. Furthermore, migration of inflammation cells and induction heat shock protein 70 (HSP70) were observed. Irradiation of the skin using a pulsed laser caused an enhanced permeability of the stratum corneum without an increase in skin temperature, migration of inflammation cells, or HSP70 induction. This effect is due to the pulsed-laser irradiation increasing the temperature of a limited part of the skin surface. Thus, the physiological response of skin is dependent on the type of laser light used. It is anticipated that this phenomenon will find wide application in such applications as, for example, general transdermal protein delivery and transdermal vaccination.

Spectroscopic analysis of two distinct equilibrium states for the exchange reaction of sodium cholate and oligo-DNA on single-walled carbon nanotubes.

Understanding the quantitative analysis of the transition adsorption structures of molecules on single-walled carbon nanotubes (SWNTs) is of importance from the point of view of both fundamental science and applications of nanotubes. Absorption spectroscopy reveals that two different equilibrium states are existent for the exchange reaction of sodium cholate (SC) and oligo-DNA (single-stranded 20-mer cytosine) on SWNTs. This is derived from the transitions of the adsorption structures of different chirality-types of SWNTs and SC/DNA at certain SC concentrations below the critical micelle concentration of SC.

Thermodynamics on soluble carbon nanotubes: how do DNA molecules replace surfactants on carbon nanotubes?

Here we represent thermodynamics on soluble carbon nanotubes that enables deep understanding the interactions between single-walled carbon nanotubes (SWNTs) and molecules. We selected sodium cholate and single-stranded cytosine oligo-DNAs (dCn (n = 4, 5, 6, 7, 8, 10, 15, and 20)), both of which are typical SWNT solubilizers, and successfully determined thermodynamic properties (ΔG, ΔH and ΔS values) for the exchange reactions of sodium cholate on four different chiralities of SWNTs ((n,m) = (6,5), (7,5), (10,2), and (8,6)) for the DNAs. Typical results contain i) the dC5 exhibited an exothermic exchange, whereas the dC6, 8, 10, 15, and 20 materials exhibited endothermic exchanges, and ii) the energetics of the dC4 and dC7 exchanges depended on the associated chiral indices and could be endothermic or exothermic. The presented method is general and is applicable to any molecule that interacts with nanotubes. The study opens a way for science of carbon nanotube thermodynamics.

Multimode resonances in silver nanocuboids.

A rich variety of dipolar and higher order plasmon resonances have been predicted for nanoscale cubes and parallopipeds of silver, in contrast to the simple dipolar modes found on silver nanospheres or nanorods. However, in general, these multimode resonances are not readily detected in experimental colloidal ensembles, due primarily to the usual variation of size and shape of the particles obscuring or blending the individual extinction peaks. Recently, methods have been found to prepare silver parallopipeds with unprecedented shape control by nucleating the silver onto a tightly controlled suspension of gold nanorods (Okuno, Y.; Nishioka, K.; Kiya, A.; Nakashima, N.; Ishibashi, A.; Niidome, Y. Uniform and Controllable Preparation of Au-Ag Core-Shell Nanorods Using Anisotropic Silver Shell Formation on Gold Nanorods. Nanoscale 2010, 2, 1489-1493). The optical extinction spectra of suspensions of such monodisperse particles are found to contain multiple extinction peaks, which we show here to be due to the multimode resonances predicted by theoretical studies. Control of the radius of the nanoparticle edges is found to be an effective way to turn some of these modes on or off. These nanoparticles provide a flexible platform for the excitation, manipulation, and exploration of higher order plasmon resonances.

Supramolecular hybrid of metal nanoparticles and semiconducting single-walled carbon nanotubes wrapped by a fluorene-carbazole copolymer.

The first approach for the preparation of metal nanoparticle/semiconducting single-walled carbon nanotube (SWNT) hybrids with specified chirality is described. For this purpose, a copolymer of a fluorene derivative with two long-chain alkyl substituents and a carbazole derivative carrying a thiol group was used. The copolymer was found to selectively dissolve (7,6)- and (8,7)SWNTs, as determined by UV/Vis/NIR absorption and Raman spectroscopy and 2D photoluminescence mapping. Gold and silver nanoparticles with diameters of about 3.8 and about 3.2 nm, respectively, were readily attached along the SWNTs by means of coordination bonds between the nanoparticles and the thiol moieties on the copolymer, as revealed by atomic force and electron microscopy studies. The study provides a novel way to design and fabricate metal nanoparticle/semiconducting SWNT hybrids with specific nanotube chirality.

Controlled-release system mediated by a retro Diels-Alder reaction induced by the photothermal effect of gold nanorods.

Controlled-release systems that respond to external stimuli have received great interest for use in medical treatments such as for drug delivery to specific sites. Gold nanorods have an absorption band at the near-infrared region and convert the absorbed light energy into heat, which is known as a "photothermal effect". Therefore, gold nanorods are expected to act not only as an on-demand thermal converter for photothermal therapy but also as a controller of a drug-release system capable of responding to the near-infrared light irradiation. In this study, to construct a controlled-release system that responds to near-infrared light irradiation, we modified gold nanorods with polyethylene glycol (PEG) through Diels-Alder cycloadducts. When the modified gold nanorods were irradiated by near-infrared light, the PEG chains were released from the gold nanorods because of the retro Diels-Alder reaction induced by the photothermal effect. As a result of the PEG release, the gold nanorods formed aggregates. This type of controlled-release system coupled with the aggregate formation of the gold nanorods triggered by near-infrared light could be expanded to applications of gold nanorods in medical fields such as drug and photothermal therapy.

Effect of backbone chemical structure of polymers on selective (n,m)single-walled carbon nanotube recognition/extraction behavior.

The development of a simple and facile method to extract single-walled carbon nanotubes (SWNTs) with a specific chirality index is one of the most-crucial issues in the fundamental study and applications of the SWNTs. We have compared the selective recognition/extraction of the SWNT chirality of poly(9,10-dioctyl-9,10-dihydrophenanthrene-2,7-diyl) (2C8-PPhO) to that of poly(9,9-dioctyfluoreny1-2,7-diyl) (2C8-PFO) that are able to extract specific semiconducting SWNTs free of any metallic SWNTs. Vis/NIR absorption, 2D photoluminescence, and Raman spectroscopy as well as molecular mechanical simulations were used to analyze and understand the obtained chiral selective solubilization behavior. We found that 2C8-PPhO selectively extracts and enriches the (8,6), (8,7), and (9,7)SWNTs, whose behaviors are different from that of 2C8-PFO, which preferentially extracts the (7,5), (7,6), (8,6), and (8,7)SWNTs. Our results indicate that 2C8-PPhO preferably recognizes larger-diameter SWNTs with higher chiral angles compared to those recognized by 2C8-PFO. These findings demonstrate that the difference in the non-aromatic ring numbers on the polymers results in different SWNT chirality recognition/extraction behaviors.

Sensing of oligopeptides using localized surface plasmon resonances combined with Surface-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry.

Gold nanorods were fixed on an ITO plate and used for the spectroscopic sensing and Surface-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (SALDI-MS) of oligopeptides (angiotensin I). The longitudinal surface plasmon bands of the gold nanorods responded to the 10(-10) M angiotensin solution that was cast on the ITO plate. The SALDI-MS measurements had an ultra-high sensitivity to the angiotensin on the ITO plate. A very small surface density (5 × 10(-19) mol cm(-2)) of angiotensin could be detected at m/z = 1297 with a good signal/noise ratio (S/N = 11). The ITO plate, which was modified with gold nanorods, was found to be effective in collecting angiotensin molecules adjacent to the gold nanorods, and the SALDI processes that were induced by the photoabsorption of the gold nanorods efficiently contributed to the desorption and ionization of the angiotensin.

Supramolecular hybrid of gold nanoparticles and semiconducting single-walled carbon nanotubes wrapped by a porphyrin-fluorene copolymer.

We describe the design, synthesis, and characterization of a supramolecular hybrid of gold nanometals and semiconducting single-walled carbon nanotubes (SWNTs) wrapped by a porphyrin-fluorene copolymer (1), as well as fabrication of a thin-film transistor (TFT) device using the hybrid. Photoluminescence mapping revealed that the copolymer selectively dissolved SWNTs with chirality indices of (8,6), (8,7), (9,7), (7,6), and (7,5); dissolution of (8,6), and (8,7) SWNTs was especially efficient. The solubilized SWNTs were connected to gold nanoparticles (AuNPs) via a coordination bond to prepare a supramolecular hybrid composed of AuNPs/copolymer 1-wrapped SWNTs, which were studied by atomic force and scanning and transmission electron microscopies. A fabricated TFT device using the semiconducting SWNTs/copolymer 1 shows evident p-type transport with an On/Off ratio of ~10(5). The transport properties of the TFT changed after coordination of the AuNPs with the SWNTs/copolymer 1.

Near-IR laser-triggered target cell collection using a carbon nanotube-based cell-cultured substrate.

Unique near-IR optical properties of single-walled carbon nanotube (SWNTs) are of interest in many biological applications. Here we describe the selective cell detachment and collection from an SWNT-coated cell-culture dish triggered by near-IR pulse laser irradiation. First, HeLa cells were cultured on an SWNT-coated dish prepared by a spraying of an aqueous SWNT dispersion on a glass dish. The SWNT-coated dish was found to show a good cell adhesion behavior as well as a cellular proliferation rate similar to a conventional glass dish. We discovered, by near-IR pulse laser irradiation (at the laser power over 25 mW) to the cell under optical microscopic observation, a quick single-cell detachment from the SWNT-coated surface. Shockwave generation from the irradiated SWNTs is expected to play an important role for the cell detachment. Moreover, we have succeeded in catapulting the target single cell from the cultured medium when the depth of the medium was below 150 µm and the laser power was stronger than 40 mW. The captured cell maintained its original shape. The retention of the genetic information of the cell was confirmed by the polymerase chain reaction (PCR) technique. A target single-cell collection from a culture medium under optical microscopic observation is significant in wide fields of single-cell studies in biological areas.

Controlled-release system of single-stranded DNA triggered by the photothermal effect of gold nanorods and its in vivo application.

Gold nanorods have strong absorption bands in the near-infrared region, in which light penetrates deeply into tissues. The absorbed light energy is converted into heat by gold nanorods, the so-called 'photothermal effect'. Hence, gold nanorods are expected to act not only as on-demand thermal converters for photothermal therapy but also as controllers of a drug-release system responding to irradiation by near-infrared light. To achieve a controlled-release system that can be triggered by light irradiation, double-stranded DNA (dsDNA) was modified on gold nanorods. When the dsDNA-modified gold nanorods were irradiated by near-infrared light, the single-stranded DNA (ssDNA) was released from gold nanorods due to the photothermal effect. The amount of released ssDNA was dependent upon the power and exposure time of light irradiation. Release of ssDNA was also observed in tumors grown on mice after light irradiation. Such a controlled-release system of oligonucleotide triggered by the photothermal effect could expand the applications of gold nanorods that have unique optical characteristics in medicinal fields.

Rational concept to recognize/extract single-walled carbon nanotubes with a specific chirality.

Single-walled carbon nanotubes (SWNTs) have remarkable and unique electronic, mechanical, and thermal properties, which are closely related to their chiralities; thus, the chirality-selective recognition/extraction of the SWNTs is one of the central issues in nanotube science. However, any rational materials design enabling one to efficiently extract/solubilize pure SWNT with a desired chirality has yet not been demonstrated. Herein we report that certain chiral polyfluorene copolymers can well-recognize SWNTs with a certain chirality preferentially, leading to solubilization of specific chiral SWNTs. The chiral copolymers were prepared by the Ni(0)-catalyzed Yamamoto coupling reaction of 2,7-dibromo-9,9-di-n-decylfluorene and 2,7-dibromo-9,9-bis[(S)-(+)-2-methylbutyl]fluorene comonomers. The selectivity of the SWNT chirality was mainly determined by the relative fraction of the achiral and chiral side groups. By a molecular mechanics simulation, the cooperative interaction between the fluorene moiety, alkyl side chain, and graphene wall were responsible for the recognition/dissolution ability of SWNT chirality. This is a first example describing the rational design and synthesis of novel fluorene-based copolymers toward the recognition/extraction of targeted (n, m) chirality of the SWNTs.

Ultrafast spectroscopy and coherent acoustic phonons of Au-Ag core-shell nanorods.

We performed the first investigations of coherent acoustic phonons in Au-Ag core-shell nanorods, which were compared with the results of parental Au nanorods. Both breathing and extensional modes were observed in Au-Ag core-shell nanorods with ~11 nm Ag shell while only extensional modes were detected in other core-shell nanorods with 4-7 nm Ag shell. Young's modulus estimated from the oscillation period of extensional modes was found to be larger for Au-Ag core-shell nanorods with ~4 nm Ag shell, as compared with that of Au nanorods. The value of Young's modulus decreases with the increase of the Ag shell thickness and finally becomes smaller than that of Au nanorods. This phenomenon is interpreted in terms of the surface effects and the existence of grain boundaries in the lattice structure of Ag shell.