Near-field optical imaging of plasmon modes in gold nanorods

We have investigated optical properties of single gold nanorods by using an apertured-type scanning near-field optical microscope. Near-field transmission spectrum of single gold nanorod shows several longitudinal surface plasmon resonances. Transmission images observed at these resonance wavelengths show oscillating pattern along the long axis of the nanorod. The number of oscillation increases with decrement of observing wavelength. These spatial characteristics were well reproduced by calculated local density-of-states maps and were attributed to spatial characteristics of plasmon modes inside the nanorods. Dispersion relation for plasmons in gold nanorods was obtained by plotting the resonance frequencies of the plasmon modes versus the wave vectors obtained from the transmission images.     

High-resolution apertureless near-field optical imaging using gold nanosphere probes

An apertureless near-field scanning optical microscope (ANSOM) that utilizes the enhanced field around a gold nanosphere, which is attached to the end of an atomic force microscope (AFM) tip, is used to image the local dielectric constant of the patterned metallic surfaces and local electric field around plasmonic nanosphere samples. A colloidal gold nanosphere (approximately 50 nm diameter) is linked to the extremity of the conventional etched-silicon probe. The scattering of laser radiation (633 or 532 nm) is modulated by the oscillating nanosphere-functionalized silicon tip, and the scattered radiation is detected. The approach curve (scattering intensity as a function of the tip-sample distance), the polarization dependence (scattering intensity as a function of the excitation polarization direction), and ANSOM image contrast confirm that the spherical nanosphere attached to the silicon tip acts as a point dipole that interacts with the sample surface via a dipole-dipole coupling, in which the dipole created by the field at the tip interacts with its own image dipole in the sample. The image obtained with the nanoparticle functionalized tip provides a dielectric map of the sample surface with a spatial resolution better than 80 nm. In addition, we show that the functionalized tip is capable of imaging the local electric field distribution above the plasmonic nanosphere samples. Overall, the result shows that high-resolution ANSOM is possible without the aid of the lightning-rod effect. With an improved tip-fabrication method, we believe that the method can provide a versatile high-resolution chemical imaging that is not available from usual forms of ANSOM.     

核酸适配子共轭金纳米粒子探针成像朊蛋白细胞内在化途径

将巯基修饰的核酸适配子(aptmer)偶联到金纳米粒子(AuNPs)表面,制备出朊蛋白特异性的Apt-AuNPs纳米光学探针,并成功应用到细胞表面朊蛋白的光散射成像和电子透射显微成像分析.通过对Apt-AuNPs探针进入细胞的途径及其在细胞内命运的进一步研究表明,窖蛋白介导的内吞作用可能是其进入细胞的一个重要途径.Apt-AuNPs纳米探针制备简单、成本低廉,可能被广泛应用于生物医学成像领域.     

Raman reporter-coated gold nanorods and their applications in multimodal optical imaging of cancer cells

We report the preparation of a kind of surface-enhanced Raman scattering (SERS) tags and explore their applications in multifunctional optical imaging of cancer cells. The proposed nanoparticles (SERS tags) are prepared by connecting dye molecules directly onto the surfaces of gold nanorods through Au–S or Au–N interactions. The dye molecules are used as Raman reporters, while gold nanorods are used as enhanced materials due to their localized surface plasmon resonance effect. Multilayered polymers are further coated onto the surfaces of the nanoparticles to reach better stability and biocompatibility. Gold nanorods with different aspect ratios and different dye molecules conjugated are compared in order to achieve the diversity of SERS tags and find out the optimized condition of SERS tags with the highest signal intensity. Our experiments show that the resulting nanoparticles, which are uptaken by cancer cells, can provide not only dark field cells images but also multiplexing SERS images.     

Plasmon mode imaging of single gold nanorods

We have investigated two-photon-induced photoluminescence images and spectra of single gold nanorods by using an apertured scanning near-field optical microscope. The observed PL spectrum of single gold nanorod can be explained by the radiative recombination of the electron-hole pair near the X and L symmetry points. PL images reveal characteristic features reflecting an eigenfunction of a specific plasmon mode as well as electric field distributions around the nanorod.     

Preparation and optical properties of worm-like gold nanorods

A type of worm-like nanorods was successfully synthesized through conventional gold nanorods reacting with Na2S2O3 or Na2S. The generated worm-like gold nanorods comprise shrunk nanorod cores and enwrapped shells. Therefore, a gold-gold sulfide core-shell structure is formed in the process, distinguishing from their original counterparts. The formation of the gold chalcogenide layers was confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy. Experimental results showed that the thickness of the gold chalcogenide layers is controllable. Since the increase of shell thickness and decrease of gold nanorod core take place simultaneously, it allows one to tune the plasmon resonance of nanorods. Proper adjustment of reaction time, temperature, additives and other experimental conditions will produce worm-like gold nanorods demonstrating desired longitudinal plasmon wavelength (LPW) with narrow size distributions, only limited by properties of starting original gold nanorods. The approach presented herein is capable of selectively changing LPW of the gold nanorods. Additionally, the formed worm-like nanorods possess higher sensitive property in localized surface plasmon resonance than the original nanorods. Their special properties were characterized by spectroscopic methods such as Vis-NIR, fluorescence and resonance light scattering. These features imply that the gold nanorods have potential applications in biomolecular recognition study and biosensor fabrications.     

Surface modification of cetyltrimethylammonium bromide-capped gold nanorods to make molecular probes

A chemical procedure to replace the cetyltrimethylammonium bromide (CTAB) cap on gold nanorods (GNRs) fabricated through seed-mediated growth with organothiol compounds [3-animo-5-mercapto-1,2,4-triazole (AMTAZ) and 11-mercaptoundecaonic acid (MUDA)] was developed to reduce the cytotoxity of GNRs and facilitate further biofunctionalization. Compared to phosphatidylcholine (PC) modification, our procedure yields stable GNRs that are biocompatible and suitable for whole-cell studies. The PC-, AMTAZ-, and MUDA-activated GNRs all showed low cytotoxicity. By choosing different organothiols, net positive or negative charges could be created on the nanorod surface, for different applications. Gold nanorod molecular probes (GNrMPs) were fabricated by subsequent attachment of antibodies to the activated GNRs and were used to visualize and detect cell surface biomarkers in normal and transformed human breast epithelial cells, demonstrating the potential of developing novel biosensors using gold nanorods. The sensitivity of GNrMPs made from organothiol-activated GNRs is considerably higher than that of CTAB/PC-activated GNRs, demonstrating that the protocol reported here is favored in developing molecular probes using GNRs.     

One-step continuous synthesis of biocompatible gold nanorods for optical coherence tomography

We present a novel one-step flow process to synthesize biocompatible gold nanorods with tunable absorption and biocompatible surface ligands. Photothermal optical coherence tomography (OCT) of human breast tissue is successfully demonstrated using tailored gold nanorods designed to have strong absorption in the near-infrared range.     

Cationic helicenes as selective G4 DNA binders and optical probes for cellular imaging

The important role that G-quadruplex DNA (G4 DNA) structures play in regulating biological processes is becoming widely recognised. These structures have also been proposed to be attractive drug targets. Therefore, there has been significant interest in developing small molecules that can selectively bind to G4 DNA over other topologies. In this paper we investigate the interaction between DNA and helical compounds (helicenes) based on a central carbocation trisubstituted with aromatic rings. We show that the non-planar structure of these helicenes results in a significantly reduced affinity for dsDNA when compared to their planar analogues, whilst maintaining a high affinity for G4 DNA. Additionally, the right- and left-handed enantiomers of one of these helicenes recognise the chiral DNA environments of G4 and dsDNA differently. We show that upon DNA binding the helicenes display a fluorescence switch-on effect, which we have successfully used for cellular imaging in live and fixed U2OS cells, staining mitochondria and the nucleus, respectively.

G-quadruplex DNA (G4 DNA) structures are selectively recognised by helical optical probes.     

Glucose oxidase-functionalized fluorescent gold nanoclusters as probes for glucose

Creation and application of noble metal nanoclusters have received continuous attention. By integrating enzyme activity and fluorescence for potential applications, enzyme-capped metal clusters are more desirable. This work demonstrated a glucose oxidase (an enzyme for glucose)-functionalized gold cluster as probe for glucose. Under physiological conditions, such bioconjugate was successfully prepared by an etching reaction, where tetrakis (hydroxylmethyl) phosphonium-protected gold nanoparticle and thioctic acid-modified glucose oxidase were used as precursor and etchant, respectively. These bioconjugates showed unique fluorescence spectra (λ_{em max} = 650 nm, λ_{ex max} = 507 nm) with an acceptable quantum yield (ca. 7%). Moreover, the conjugated glucose oxidase remained active and catalyzed reaction of glucose and dissolved O₂ to produce H₂O₂, which quenched quantitatively the fluorescence of gold clusters and laid a foundation of glucose detection. A linear range of 2.0 × 10⁻⁶–140 × 10⁻⁶ M and a detection limit of 0.7 × 10⁻⁶ M (S/N = 3) were obtained. Also, another horseradish peroxidase/gold cluster bioconjugate was produced by such general synthesis method. Such enzyme/metal cluster bioconjugates represented a promising class of biosensors for biologically important targets in organelles or cells.     

Synthesis and characterization of glucosamine-bound near-infrared probes for optical imaging

[structure: see text] Two novel near-infrared (NIR) fluorescent probes have been synthesized by linking a carbocyanine fluorophore and glucosamine through different linkers. These probes demonstrated a high quantum yield, low cytotoxicity, reversible pH-dependent fluorescence in the physiological pH range, and a decreased aggregation tendency in aqueous solutions. In vitro NIR optical imaging studies revealed cellular uptake and strong intracellular NIR fluorescence of these two probes in four breast epithelial cell lines.     

CeO2 nanorods and gold nanocrystals supported on CeO2 nanorods as catalyst

The formation mechanism of uniform CeO2 structure at the nanometer scale via a wet-chemical reaction is of great interest in fundamental study as well as a variety of applications. In this work, large-scale well-crystallized CeO2 nanorods with uniform diameters in the range of 20-30 nm and lengths up to tens of micrometers are first synthesized through a hydrothermal synthetic route in 5 M KOH solution at 180 degrees C for 45 h without any templates and surfactants. The nanorod formation involves dehydration of CeO2 nanoparticles and orientation growth along the 110 direction in KOH solution. Subsequently, gold nanoparticles with crystallite sizes between 10 and 20 nm are loaded on the surface of CeO2 nanorods using HAuCl4 solution as the gold source and NaBH4 solution as a reducing agent. The synthesized Au/CeO2 nanorods demonstrate a higher catalytic activity in CO oxidation than the pure CeO2 nanorods.     

Hematite spindles with optical functionalities: growth of gold nanoshells and assembly of gold nanorods

The layer-by-layer (LBL) assembly method, combined with the seeded growth technique, have been used to deposit gold shells on the surface of hematite (alpha-Fe(2)O(3)) spindles. While the LBL method yields dense coatings of preformed Au nanoparticles, when AuCl(-)(4) ions are further reduced by a mild reducing agent, thicker, rough nanostructured shells can be grown. The deposition process was monitored by TEM and UV-visible spectroscopy, demonstrating a gradual change in the optical features of the colloids as the surface is more densely covered. The particles so-prepared can find useful applications in cancer therapy and as SERS substrates. Additionally, we show that Au nanorods can be assembled on hematite spindles, providing a flexible way to tune the optical properties of the resulting composite colloids.     

Single particle technique for one-step homogeneous detection of cancer marker using gold nanoparticle probes

In this paper, we reported a single particle technique for the one-step homogeneous immunoassay of a cancer marker by resonance light scattering correlation spectroscopy (RLSCS). The setup of RLSCS was similar to fluorescence correlation spectroscopy (FCS), and its principle was based on measuring the resonance light scattering fluctuations in a small volumes (less than 1 fL) due to Brownian motion of single particles. In homogeneous immunoassay, we used a sandwich strategy and conjugated two different antibodies (Ab) with gold nanoparticles (GNPs) respectively. When two different GNPs labeled with antibodies are mixed in a sample containing antigen (Ag) targets, the binding of targets will cause GNPs to form dimers (or oligomers), which leads to the significant increase in the characteristic diffusion time of GNPs in the detection volume. The RLSCS method can sensitively detect the change in the characteristic diffusion time of GNPs before and after immune reactions. We used this technology in homogeneous immunoassays for the liver cancer biomarker alpha-fetoprotein (AFP). The conditions of the immune reaction were investigated systematically. In the optimal conditions, the linear range of this assay is from 1 pM to 1 nM and the detection limit is 1 pM for AFP. This new method was successfully applied for the direct determination of AFP levels in sera from healthy subjects and cancer patients. Our results were in good agreement with ELISA assays.     

Protein-templated gold nanoclusters as fluorescence probes for the detection of methotrexate

In this contribution, bovine serum albumin stabilized gold nanoclusters as novel fluorescent probes were successfully utilized for the detection of methotrexate for the first time. Our prepared gold nanoclusters exhibited strong emission with peak maximum at 633.5 nm. However, the addition of methotrexate induced the strong fluorescence intensity of the gold nanoclusters to decrease. The decrease in fluorescence intensity of the gold nanoclusters caused by methotrexate allowed the sensitive detection of methotrexate in the range of 0.0016 μg mL(-1) to 24 μg mL(-1). The detection limit for methotrexate is 0.9 ng mL(-1) at a signal-to-noise ratio of 3. The present sensor for methotrexate detection possessed a low detection limit and wide linear range. In addition, the real samples were analyzed with satisfactory results.     

Synthesis of Pt@Fe2O3 nanorods as MRI probes for in vivo application

Magnetic Fe(2)O(3) nanorods with low cell toxicity were successfully synthesized via a wet-chemical method. In vivo studies with a rabbit model show that the nanorods exhibit excellent T(2) signal enhancement. This work demonstrates that magnetic nanorods may provide a new type of MR enhancement agent for use in biomedical applications.     

Near-field two-photon-induced photoluminescence from single gold nanorods and imaging of plasmon modes

We investigated the two-photon-induced photoluminescence properties of single gold nanorods by scanning near-field spectroscopy. The process was found to be initiated by a sequential one-photon absorption for creating a pair of an electron and a hole in the sp and d bands. Photoluminescence is then radiated when the electron near the Fermi surface recombines with the hole near the X and L symmetry points. The polarization characteristics of emitted photons from the X and L regions were found to be different. These characteristics can be understood by the crystalline structure and the band structure of the gold nanorod. We found characteristic spatial oscillatory features along the long axis of the nanorods in photoluminescence excitation images. The images were well reproduced by density-of-states maps of the nanorods calculated with Green's dyadic method and were attributed to the spatial characteristics of the wave functions of the plasmon modes inside the nanorods.