Aptamer‐Assisted Assembly of Gold Nanoframe Dimers

The assembly of nanoframe dimers assisted by aptamer‐functionalized smaller spherical gold nanoparticles as prospective surface‐enhanced Raman scattering (SERS) biotraps for riboflavin, an important molecule for biological electron transfer reactions, is reported. In this approach, the aptamer‐coated gold nanoparticles designed for selective binding of riboflavin also serve as the electrostatic driver for nanoframe dimerization in dilute solutions. The gold nanoframe dimers provide unique conditions for plasmonic coupling in a hot spot with sufficient space for the binding of bulky biomolecules. The use of an aptamer allows for highly selective binding of the targeted analyte as compared with conventional organic ligands with excellent low detection limit of one micromole of riboflavin.     

A three‐dimensional surface‐enhanced Raman scattering substrate: Au nanoparticle supramolecular self‐assembly in anodic aluminum oxide template

A three‐dimensional surface‐enhanced Raman scattering (SERS) substrate via the self‐assembly of properly sized Au nanoparticles in anodic aluminum oxide templates was designed and prepared. Au nanoparticles first underwent hydrophobic surface modification. Then, the hydrophobic Au nanoparticles self‐assembled, aggregated and formed many hot spots in the anodic aluminum oxide templates through a supramolecular interaction. We chose thiophenol as a probe molecule to evaluate the SERS enhancement ability of this three‐dimensional substrate. The enhancement factor was calculated to be 4.6 × 10⁶ under the radiation of a 785‐nm laser. By further comparing SERS signals from different points on the same substrate, we confirmed that this substrate possessed good reproducibility and could be applied for SERS detection. Copyright © 2011 John Wiley & Sons, Ltd.     

Detection of protein molecules by surface‐enhanced Raman spectroscopy‐based immunoassay using 2–5 nm gold nanoparticle lables

Here we report the synthesis of 2–5 nm size gold nanoparticle labels for surface‐enhanced Raman Spectroscopy (SERS) based immunoassay to detect protein molecules. The Au nanoparticles were conjugated with fluorescein isothiocyanate (FITC) and goat anti‐h‐IgG (immunoglobin) and the resultant particles were used for the detection of h‐IgG. Commercially available nitrocellulose strip and silver enhancement method were used for SERS‐based immunoassays. The FITC acts as a Raman probe, and vibrational fingerprint of this molecule was used for the detection of h‐IgG in concentration ranging from 1 to 100 ng/µl. Our Raman probe is robust and small in size and has high water solubility with minimum steric effect during antigen–antibody binding. Copyright © 2007 John Wiley & Sons, Ltd.     

Probing Chemical and Mechanical Nanodomains in Copolymer Nanorods with Correlative Atomic Force Microscopy—Nano‐correscopy

The interplay between size, shape, mechanical properties, and surface chemistry of nanoparticles orchestrates cellular internalization, toxicity, circulation time, and biodistribution. Therefore, the safety of nanoparticles hinges on our ability to quantify nanoscale physicochemical characteristics. Current characterization tools, due to their limited resolution, are unable to map these properties correlatively at nanoscale. An innovative use of atomic force microscopy‐based techniques, namely nano‐correscopy, overcomes this limitation and offers multiprobe capability to map mechanical (viscous and elastic) and chemical domains of nanoparticles correlatively. The strengths of this approach are demonstrated using polymer composite nanorods: m‐PEG‐PLGA ((m‐PEG–methoxy‐poly (ethylene glycol)‐b‐poly (lactic‐co‐glycolic) acid). Precise distribution of PLGA (monomers of lactide and glycolide) and poly(ethylene glycol) (PEG) polymer across nanorods is identified. The hydrophobic lactide component is found predominantly at the apex, while hydrophilic glycolide and PEG assembled at the body of the nanorods and correlate with a gradient of nanomechanical properties. New knowledge of how both nanochemical domains and nanomechanical properties are distributed across the nanorod will allow elucidating the interactions of nanorods with the proteins and biomolecules in the future, which will directly influence the fate of nanorods in vivo and will guide new synthesis methods.     

Size‐Dependence of the Melting Temperature of Individual Au Nanoparticles

Nanoparticles have an immense importance in various fields, such as medicine, catalysis, and various technological applications. Nanoparticles exhibit a significant depression in melting point as their size goes below ≈10 nm. However, nanoparticles are frequently used in high temperature applications such as catalysis where temperatures often exceed several 100 degrees which makes it interesting to study not only the melting temperature depression, but also how the melting progresses through the particle. Using high‐resolution transmission electron microscopy, the melting process of gold nanoparticles in the size range of 2–20 nm Au nanoparticles combined with molecular dynamics studies is investigated. A linear dependence of the melting temperature on the inverse particle size is confirmed; electron microscopy imaging reveals that the particles start melting at the surface and the liquid shell formed then rapidly expands to the particle core.     

An Improved Method for Site‐Specific End Modification of Zeolite L for the Formation of Zeolite L and Gold Nanoparticle Self‐Assembled Structures

The ability to site‐selectively modify micro‐ and nanosized particles has allowed for directed self‐assembly in two and three dimensions. Site‐selective modification of particles can be a complicated task requiring the pre‐organization of particles or enhanced particle fabrication methods. The aluminum silicate, zeolite L has been reported to undergo site‐specific modification at the zeolite channel entrances, post‐fabrication in a solution‐based method. The process by which the channel entrances are site selectively modified is explored here. The preliminary step of charging the zeolite channels with aqueous acid allows for catalysis of covalent bond formation at the channel entrances. Three new end‐specific modification reagents are described based on silanol and silyl ether functional groups. These reagents are purified by column chromatography and characterized by¹H NMR spectroscopy and high resolution mass spectrometry (HRMS); they provide for reliable end modification of zeolites L. Preferential reactivity at the channel entrances is also observed. The utility of the approach is demonstrated by modifying zeolite L with adamantane at the channel entrances. Site‐specific self‐assembly with β‐cyclodextrin coated gold nanoparticles can be triggered with a chemical stimulus. The resulting multivalent host‐guest interactions give gold clustered nanoparticles at the ends of the micrometer‐sized zeolites.     

Designing Zwitterionic SiO2NH2‐Au Particles with Tunable Patchiness using Wrinkles

A facile template‐based approach toward zwitterionic SiO₂NH₂‐Au patchy particles is presented. Therefore, wrinkle templates prepared by stress release in a bilayer system comprised of an elastic PDMS fundament and a thin SiO_x top layer are used. After aligning positively charged, amine‐functionalized silica particles in wrinkle grooves, their surfaces are partially modified with negatively charged gold nanoparticles in an electrostatic adsorption step. Patchiness is precisely controlled by the degree of immersion of the initial particles into wrinkles of varying dimensions. By ultrasonication or wetting with a water droplet, patchy particles are easily released from the substrate‐yielding particles with two oppositely charged hemispheres. Interfacial tension measurements prove the surface activity of the SiO₂NH₂‐Au particles in an oil/water system and are explained in the view of the Janus‐type surface charges of the particles and the charge of the oil/water interface.     

Surface enhanced Raman scattering of molecules related to highly ordered gold cavities

We presented a controlled particles‐in‐cavity (PIC) pattern for surface‐enhanced Raman scattering (SERS) detection. The periodic gold cavity array was fabricated by electrodeposition using highly ordered polystyrene spheres as a template. The as‐prepared gold cavities can be used as a SERS active substrate with significant spectral enhancement and reproducibility, which was evaluated by SERS signals using 4‐mercaptobenzoic acid (4‐MBA) as probe molecules. The surface of these gold cavities was further functionalized with cetyltrimethylammonium bromide molecules, which may immobilize the 4‐MBA‐modified silver nanoparticles in the gold cavity to form a PIC structure via the electrostatic interaction. We have demonstrated that there exists a pH window for the immobilization of the nanoparticles inside cavities. Therefore, the silver nanoparticles can be selectively immobilized into the functionalized gold cavities under the optimized pH value of the media. Further enhancement of the Raman scattering of the labeled molecules can be achieved due to the interconnection between the silver nanoparticles and gold cavity. Copyright © 2013 John Wiley & Sons, Ltd.     

Visible‐Light‐Induced Directed Gold Microwires by Self‐Organization of Nanoparticles on Aspergillus Niger

A directional point‐to‐point growth of microwires of gold nanoparticles (AuNPs) self‐organized on Aspergillus niger (A. niger) templates by utilizing positive phototropic fungal response to different spectral ranges of visible light is reported. A. niger serves as a living template for the self‐organization of monosodium glutamate (MSG) capped gold colloids under controlled nutrient trigger and appropriate light, temperature, and humidity conditions. The experimental results show that control of these parameters eliminates the need for any microchannels for the directional growth of microwires. The growth rate of fungal hyphae increases exponentially under light illumination compared to its growth in the dark under similar conditions. White light is found to be most suitable to trigger the directional growth. Gold microwires of about 1 to 2 μm diameter and length exceeding 1 mm are grown within a week with a maximum divergence of 40–50° from the light path regardless of the wavelength of the light irradiation. Phototropic response of fungi has been investigated intensively over the last three decades, but this is the first report on the collective use of microbial tropism and directed biomimetic self‐organization of metallic nanoparticles on living organisms.     

Single‐molecule detection of thionine on aggregated gold nanoparticles by surface enhanced Raman scattering

We report observations of single‐molecule detection of thionine and its dynamic interactions on aggregated gold nanoparticle clusters using surface enhanced Raman scattering (SERS). Spectral intensities were found to be independent of the size of Au nanoparticles studied (from 17 to 80 nm) at thionine concentration below 10⁻¹² M or at single‐molecule concentration levels. Raman line separations and, in particular, spectral fluctuations and blinking were also observed, suggesting temporal changes in single molecular motion and/or arrangements of thionine on Au nanoparticle surfaces. In contrast, by using dispersed Au nanoparticles, only ensemble SERS spectra could be observed at relatively high concentrations (> 10⁻⁸ M thionine), and spectral intensities varied with the size of Au nanoparticles. Copyright © 2007 John Wiley & Sons, Ltd.     

Destabilization of Thiolated Gold Clusters for the Growth of Single‐Crystalline Gold Nanoparticles and Their Self‐Assembly for SERS Detection

Thiolate‐protected gold nanoclusters with high chemical stability are exploited extensively for fundamental research and utility in chosen applications. Here for the first time, the controlled destabilization of extraordinarily stable thiolated gold clusters for the growth of single‐crystalline gold nanoparticles (AuNPs) is demonstrated, which was achieved simply via the oxidation of surface‐protecting thiolates into disulfides by hydrogen peroxide under basic condition. By combining with our experimental observations over the entire destabilization and growth process, the new growth mechanism from clusters to AuNPs is revealed by density functional theory (DFT) calculations. It is found that the size of AuNPs decreases with the increase of hydrogen peroxide concentration due to the generation of more nuclei at the higher hydrogen peroxide concentrations. In addition, the preparation of AuNPs is tuned by changing the concentration of hydrogen peroxide, and they are self‐assembled into microspheres via an evaporation‐mediated process, which can induce strong plasmonic coupling between adjacent AuNPs for ultrasensitive surface‐enhanced Raman scattering detection. The present work demonstrates a facile route to functionalize and engineer AuNPs via controlling the reaction conditions and the ratio of precursors, and thus bring new possibilities for using more clusters as precursors to construct novel nano/microstructures for various applications.     

In Vitro Evaluation of Non‐Protein Adsorbing Breast Cancer Theranostics Based on 19F‐Polymer Containing Nanoparticles

Eight fluorinated nanoparticles (NPs) are synthesized, loaded with doxorubicin (DOX), and evaluated as theranostic delivery platforms to breast cancer cells. The multifunctional NPs are formed by self‐assembly of either linear or star‐shaped amphiphilic block copolymers, with fluorinated segments incorporated in the hydrophilic corona of the carrier. The sizes of the NPs confirm that small circular NPs are formed. The release kinetics data of the particles reveals clear hydrophobic core dependence, with longer sustained release from particles with larger hydrophobic cores, suggesting that the DOX release from these carriers can be tailored. Viability assays and flow cytometry evaluation of the ratios of apoptosis/necrosis indicate that the materials are non‐toxic to breast cancer cells before DOX loading; however, they are very efficient, similar to free DOX, at killing cancer cells after drug encapsulation. Both flow cytometry and confocal microscopy confirm the cellular uptake of NPs and DOX‐NPs into breast cancer cells, and in vitro ¹⁹F‐MRI measurement shows that the fluorinated NPs have strong imaging signals, qualifying them as a potential in vivo contrast agent for ¹⁹F‐MRI.     

Analysis of self‐repair mechanisms of Phaseolus vulgaris var. saxa using near‐infrared surface‐enhanced Raman spectroscopy

We used surface‐enhanced Raman spectroscopy (SERS) to investigate ultrastructural changes in cell‐wall composition during the self‐repair of lacerated hypocotyls of Phaseolus vulgaris var. saxa. A detailed study of self‐repair mechanisms requires localized information about cell‐wall structure and morphology in addition to the chemical cell‐wall composition. Characteristic Raman and SER spectra yielded two‐dimensional maps of cross sections of P. vulgaris var. saxa visualizing chemical compositions in the walls of different cell types and during various repair phases. SERS substrate particles were produced by the reduction of gold chloride on the plant tissue surface and characterized with absorption spectroscopy, scanning electron microscopy and energy‐dispersive X‐ray spectroscopy. The SERS results were compared with stained cross sections of the same plant using dark‐field microscopy with focus on lignin and suberin contents in repairing cells. In addition, SERS measurements revealed Au cyanide compounds on the cell surface, indicating the formation of hydrogen cyanide during the self‐repair phase. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of Self‐Stabilized Poly(N‐(3‐Amidino)‐Aniline) Particles and their CO2‐Responsive Properties

Novel CO₂‐responsive conductive polymer particles based on poly(N‐(3‐amidino)‐aniline) (or PNAAN) are reported in this work. A CO₂‐responsive N‐(3‐amidino)‐aniline (NAAN) monomer is firstly synthesized with the pendant amidine group at the meta‐position of aniline (AN) and subsequently polymerized into the PNAAN polymer by chemical oxidation. Self‐assembly of PNAAN in turn forms the polymer particles. In the strong or weak acid media, the amidine group protonates into cationic amidinium and self‐stabilizes the PNAAN particles without the use of any stabilizers. The reaction media are found to affect the polymerization rate and self‐assembly of particles, and hence the size and size distribution of the resultant particles. The particles synthesized in strong basic media show CO₂‐responsvie properties since the H⁺ released by dissolved CO₂ (dCO₂) can protonate the amidine group into hydrophilic amidinium group and result in swelling of the PNAAN particles. Zeta‐potential measurements show the reversible change of particle surface charges in the presence and absence of dCO₂. Dynamic light scattering (DLS) measurements show the particle size linearly changed with dCO₂ concentration in the range of 5 × 10^?4 and 2.5 × 10^?2 atm. This is the first reported CO₂‐responsive polyaniline (PANI) particles for dCO₂ sensing or reversible fixation of CO₂.     

Correlation between structure and optoelectronic properties in a two‐dimensional nanoparticle assembly

The optical properties of two‐dimensional assemblies of metal nanoparticles are strongly influenced by the morphological configuration of the metal particles in the layer. Therefore, we correlate the structural and optical properties of two‐dimensional, hexagonal gold nanoparticle arrays. We characterize the structure of the arrays using grazing‐incidence small angle X‐ray scattering (GISAXS). From the GISAXS pattern, we determine the size of the gold particles as well as the lattice spacing of the hexagonal assembly. Based upon these parameters we calculate the dielectric function of the gold particle array using the Maxwell–Garnett effective medium theory. We further deduce the absorption spectrum which closely follows the measured absorption and photoconductance spectrum. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Self-Assembly of Gold Nanoparticles on Nanometre-Patterned Surface

The self-assembly processes of gold nanoparticles on nanometre-step-patterned Si surface and polished Si surface are investigated by the convective self-assembly method. The convective self-assembly method is used to deposit the colloids dispersed in benzene onto the substrates. The SEM results show that the configurations of the gold arrays depend on the surface morphology of the substrates. On the nanometre-step-patterned Si surface, the nanoparticles self assemble into parallel lines, and the distance between the neighbouring lines is around 35 nm. On the polished Si surface the nanoparticles form compact domains. In each domain the particles are closepacked in a two-dimensional hexagonal superlattice and are separated by uniform distances. The analysis shows that on the nanometre-step-patterned Si surface, the steps play critical roles in the self-assembly process of gold nanoparticles. The capillary force from the steps drives the particles to lines along the steps. Therefore, the particles tend to self-assemble into one-dimensional line structures when the solvent evaporates. For the polished Si substrate there is a little difference that the particles form two-dimensional hexagonal superlattices without the directional confinement.     

Ordered Networks of Gold Nanoparticles Crosslinked by Dithiol‐Oligomers

Controlled aggregation of nanoparticles into superlattices is a grand challenge in material science, where ligand based self‐assembly is the dominant route. Here, the self‐assembly of gold nanoparticles (AuNPs) that are crosslinked by water soluble oligo‐(ethylene glycol)‐dithiol (oEG‐dithiol) is reported and their 3D structure by small angle X‐ray scattering is determined. Surprisingly, a narrow region is found in the parameter space of dithiol linker‐length and nanoparticle size for which the crosslinked networks form short‐ranged FCC crystals. Using geometrical considerations and numerical simulations, the stability of the formed lattices is evaluated as a function of dithiol length and the number of connected nearest‐neighbors, and a phase diagram of superlattice formation is provided. Identifying the narrow parameter space that allows crystallization facilitates focused exploration of linker chemical composition and medium conditions such as thermal annealing, pH, and added solutes that may lead to superior and more robust crystals.     

碳纳米管表面金纳米颗粒的形成与结构转变

利用分子动力学模拟研究了室温下金纳米颗粒在碳纳米管表面的结构和作用能.研究结果表明,金纳米颗粒随着尺寸的增大会发生不同于孤立状态下的结构转变.当原子数小于130时,颗粒属于无序结构;当原子数大于140时,呈现面心立方晶体结构.小金纳米颗粒和碳纳米管结合紧密,相互作用能正比于面对碳纳米管的颗粒表面面积. 关键词： 金纳米颗粒 碳纳米管 分子动力学模拟     

Multifunctional Plasmonic Co‐Doped Fe2O3@polydopamine‐Au for Adsorption,Photocatalysis, and SERS‐based Sensing

A new type of multifunctional plasmonic nanoparticles, cobalt‐doped Fe₂O₃@polydopamine‐Au (Co‐Fe₂O₃@PDA‐Au), is fabricated via coating PDA through self‐polymerization onto Co‐Fe₂O₃ and further loading gold nanoparticles by in situ reduction onto the surface of PDA shell. Benefiting from the universal adhesive ability of PDA and negative zeta potetntial of the composite, the Co‐Fe₂O₃@PDA‐Au shows strong adsorptivity for cationic dyes. The presence of gold nanoparticle with the diameter of 15 nm in the Co‐Fe₂O₃@PDA‐Au system promotes surface‐enhanced Raman scattering (SERS) activity with an impressive detection limit of 1 × 10^?6 m . Thanks to the synergistic effect of the light harvesting of PDA, the surface plasmon resonance of Au, and the electron conductibility of PDA and Au, the Co‐Fe₂O₃@PDA‐Au exhibits an enhanced photocatalytic activity comparing with unmodified Co‐Fe₂O₃. All the above‐mentioned functions enable Co‐Fe₂O₃@PDA‐Au to be a multifunctional material system for various applications toward environmental pollutants.     

Surface‐enhanced resonance Raman spectroscopic characterization of cytochrome c immobilized on 2‐mercaptoethanesulfonate monolayers on silver

Single‐component self‐assembled monolayers (SAMs) of mercaptoethanesulfonate (MES) on Ag surfaces were studied with surface‐enhanced resonance Raman scattering (SERRS) spectroscopy with a view to their application to immobilize (ferro)cytochrome c (cyt c). SERS studies revealed that MES molecules adopt primarily trans (T) conformation even at early stages of the SAM growth and over wide range of pH values. High accessibility of the negatively charged groups for (bio)molecules in solution makes single‐component MES SAMs suitable linkage monolayers for electrostatic attachment of cyt c, which was verified with SERRS. Cyt c was successfully anchored to MES‐coated Ag at natural (∼5), neutral, and isoelectric point (10.6) pH. At pH = 7.0 and 10.6, SERRS bands characteristic of native six‐coordinated low‐spin (6cLS) heme iron configuration were detected. Lack of buffering resulted in additional appearance of five‐coordinated high‐spin (5cHS) SERRS markers and the presence of bands indicating ferric ion. An electrostatic attraction between protein and SAM was confirmed to exclude the hydrophobic interactions involved in cyt c binding. Cyt c attached to MES SAM on Ag was found to be electroactive at neutral pH, and protein oxidation was assisted with reversible conversion of 6cLS to the non‐native 5cHS state. Alteration of heme orientation deduced from SERRS spectra upon change of redox state allowed us to propose the protein dynamics as the electron transfer rate‐limiting step. Copyright © 2010 John Wiley & Sons, Ltd.