Ordered Arrangement and Optical Properties of Silica‐Stabilized Gold Nanoparticle–PNIPAM Core–Satellite Clusters for Sensitive Raman Detection

Gold–polymer hybrid nanoparticles attract wide interest as building blocks for the engineering of photonic materials and plasmonic (active) metamaterials with unique optical properties. In particular, the coupling of the localized surface plasmon resonances of individual metal nanostructures in the presence of nanometric gaps can generate highly enhanced and confined electromagnetic fields, which are frequently exploited for metal‐enhanced light–matter interactions. The optical properties of plasmonic structures can be tuned over a wide range of properties by means of their geometry and the size of the inserted nanoparticles as well as by the degree of order upon assembly into 1D, 2D, or 3D structures. Here, the synthesis of silica‐stabilized gold–poly(N‐isopropylacrylamide) (SiO₂‐Au‐PNIPAM) core–satellite superclusters with a narrow size distribution and their incorporation into ordered self‐organized 3D assemblies are reported. Significant alterations of the plasmon resonance are found for different assembled structures as well as strongly enhanced Raman signatures are observed. In a series of experiments, the origin of the highly enhanced signals can be assigned to the interlock areas of adjacent SiO₂‐Au‐PNIPAM core–satellite clusters and their application for highly sensitive nanoparticle‐enhanced Raman spectroscopy is demonstrated.     

Inside Front Cover: One‐Dimensional Plasmon Coupling by Facile Self‐Assembly of Gold Nanoparticles into Branched Chain Networks (Adv. Mater. 21/2005)

Short, single‐particle‐wide chains and complex networks of interconnected chains are easily self‐assembled from 13 nm Au nanoparticles by inducing a surface electrostatic dipolar moment in a controlled manner. Mann and co‐workers further demonstrate both experimentally and theoretically on p. 2553 that efficient surface plasmon coupling takes place in these extensive networks, thus opening a new bottom–up approach to subwavelength optical‐waveguiding devices. The left panel in the image shows isolated 13 nm Au nanoparticles; the back panel, short linear chains; the bottom panel, complex branched network of chains; and the right panel, a graphical rendering of optical spectroscopic properties during the self‐assembly process.     

Virus‐Templated Plasmonic Nanoclusters with Icosahedral Symmetry via Directed Self‐Assembly

The assembly of plasmonic nanoparticles with precise spatial and orientational order may lead to structures with new electromagnetic properties at optical frequencies. The directed self‐assembly method presented controls the interparticle‐spacing and symmetry of the resulting nanometer‐sized elements in solution. The self‐assembly of three‐dimensional (3D), icosahedral plasmonic nanosclusters (NCs) with resonances at visible wavelengths is demonstrated experimentally. The ideal NCs consist of twelve gold (Au) nanospheres (NSs) attached to thiol groups at predefined locations on the surface of a genetically engineered cowpea mosaic virus with icosahedral symmetry. In situ dynamic light scattering (DLS) measurements confirm the NSs assembly on the virus. Transmission electron micrographs (TEM) demonstrate the ability of the self‐assembly method to control the nanoscopic symmetry of the bound NSs, which reflects the icosahedral symmetry of the virus. Both, TEM and DLS show that the NCs comprise of a distribution of capsids mostly covered (i.e., 6–12 NS/capsid) with NSs. 3D finite‐element simulations of aqueous suspensions of NCs reproduce the experimental bulk absorbance measurements and major features of the spectra. Simulations results show that the fully assembled NCs give rise to a 10‐fold surface‐averaged enhancement of the local electromagnetic field.     

Enzyme‐Responsive Nanoparticle Systems

Inorganic nanoparticles and their accompanying diverse physical properties are now virtually in routine use as imaging tools in cell‐biology. In addition to serving as excellent contrast agents, their size‐ and environment‐dependent optical and magnetic properties can be harnessed to create enzyme biosensor devices of extremely high sensitivity, whilst circumventing the numerous technical limitations associated with traditional enzyme assays. In this Research News article we discuss recent advances in field of enzyme‐responsive nanoparticle systems, where the activity of an enzyme elicits a specific response in the nanoparticle assembly to produce a signal relating to enzyme activity, focusing on three important systems: DNA‐structured nanoparticles, protein kinases and proteases.     

Three-dimensional assembly of nanoparticles from charged aerosols

The capability of assembling nanoparticles into a desired ordered pattern is a key to realize novel devices which are based not only on the unique properties of nanoparticles but also on the arrangements of nanoparticles. While two-dimensional arrays of nanoparticles have been successfully demonstrated by various techniques, a controlled way of building ordered arrays of three-dimensional (3D) nanoparticle structures remains challenging. We report that a variety of 3D nanoparticle structures can be formed in a controlled way based on the ion-induced focusing, electrical scaffold, and antenna effects from charged aerosols. Particle trajectory calculations successfully predict the whole process of 3D assembly. New surface enhanced Raman scattering substrates based on our 3D assembly were constructed as an example showing the viability of the present approach. This report extends the current capability of positioning nanoparticles on surface to another spatial dimension, which can serve as the foundation of future optical, magnetic, and electronic devices taking the advantage of multidimensions.     

Field Effect and Photoconduction in Au25 Nanoclusters Films

Quantum‐confined Au nanoclusters exhibit molecule‐like properties, including atomic precision and discrete energy levels. The electrical conductivity of Au nanocluster films can vary by several orders of magnitude and is determined by the strength of the electronic coupling between the individual nanoclusters in the film. Similar to quantum‐confined, semiconducting quantum dots, the electrical coupling in films is dependent on the size and structure of the Au core and the length and conjugation of the organic ligands surrounding it. Unlike quantum dots, however, semiconducting transport has not been reported in Au nanocluster films. Here, it is demonstrated that through a simple yet careful choice of cluster size and organic ligands, stable Au nanocluster films can electronically couple and become semiconducting, exhibiting electric field effect and photoconductivity. The molecule‐like nature of the Au nanoclusters is evidenced by a hopping transport mechanism reminiscent of doped, disordered organic semiconductor films. These results demonstrate the potential of metal nanoclusters as a solution‐processed material for semiconducting devices.     

Directing Gold Nanoparticles into Free‐Standing Honeycomb‐Like Ordered Mesoporous Superstructures

2D mesoporous materials fabricated via the assembly of nanoparticles (NPs) not only possess the unique properties of nanoscale building blocks but also manifest additional collective properties due to the interactions between NPs. In this work, reported is a facile and designable way to prepare free‐standing 2D mesoporous gold (Au) superstructures with a honeycomb‐like configuration. During the fabrication process, Au NPs with an average diameter of 5.0 nm are assembled into a superlattice film on a diethylene glycol substrate. Then, a subsequent thermal treatment at 180 °C induces NP attachment, forming the honeycomb‐like ordered mesoporous Au superstructures. Each individual NP connects with three neighboring NPs in the adjacent layer to form a tetrahedron‐based framework. Mesopores confined in the superstructure have a uniform size of 3.5 nm and are arranged in an ordered hexagonal array. The metallic bonding between Au NPs increases the structural stability of architected superstructures, allowing them to be easily transferred to various substrates. In addition, electron energy‐loss spectroscopy experiments and 3D finite‐difference time‐domain simulations reveal that electric field enhancement occurs at the confined mesopores when the superstructures are excited by light, showing their potential in nano‐plasmonic applications.     

Preparation of gold nanoparticles on silica substrate by radio frequency sputtering

Radio frequency sputtering of gold on amorphous silica substrates was used for the preparation of Au nanoparticles on SiO2. Deposition experiments were carried out in Ar plasmas under mild conditions (RF power = 5/10 W, total pressure = 0.38 mbar, substrate temperature < or = 210 degrees C), focusing in particular on the effect of sputtering time (5/30 min) and substrate temperature on gold nucleation and coalescence, with the aim of obtaining SiO2-supported Au nanoparticles characterized by precise structural and morphological features. To this aim, several analytical techniques were employed for a thorough characterization of the systems properties, including glancing incidence X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and UV-Vis absorption spectroscopy. In particular, the evolution of optical spectra, i.e., of the surface plasmon resonance peak, was used as a probe for the structural features and was related to the results obtained by other characterization techniques. Gold nanoclusters (phi approximately 4/10 nm) dispersed uniformly on silica matrices were obtained under soft conditions, with morphology ranging from island to cluster like. The obtained results make possible a careful modulation of substrate coverage and gold nanoparticle size.     

One Step Synthesis of Gold‐Loaded Radial Mesoporous Silica Nanospheres and Supported Lipid Bilayer Functionalization: Towards Bio‐Multifunctional Sensors

A simple synthetic route is developed to achieve gold functionalized radial mesoporous silica nanoparticles (Au‐MsNP) synthesized by a one step procedure fully compatible with basic conditions required for the preparation of monodispersed nanospheres. In a second step, Au‐MsNP particles have been coated with phospholipid bilayers in order to design an advanced biofunctional platform with the gold metallic nanoparticles previously grown into the pore channels and responsible for a plasmonic activity relevant for biosensing. The size of Au‐MsNP is checked by dynamic light scattering while zeta potential measurements reflect their surface charge. The particle morphology is characterized by transmission and scanning electron microscopy and the Si/Au ratios are obtained from energy dispersive X‐ray analysis. The textural properties of Au‐MsNP, specific surface area and pore size, are determined from N₂ adsorption. The supported bilayers are achieved from vesicles of different phospholipids incubated with Au‐MsNP particles. The coating efficiency is investigated by zeta potential and cryo‐ transmission electron microscopy. The plasmonic activities of bare Au‐MsNP particles and coated lipid bilayer Au‐MsNP platform are evidenced for two model systems: direct adsorption of bovine serum albumin and molecular recognition events between avidin molecules and biotin receptors integrated in the supported lipid bilayer.     

Split‐GFP: SERS Enhancers in Plasmonic Nanocluster Probes

The assembly of plasmonic metal nanoparticles into hot spot surface‐enhanced Raman scattering (SERS) nanocluster probes is a powerful, yet challenging approach for ultrasensitive biosensing. Scaffolding strategies based on self‐complementary peptides and proteins are of increasing interest for these assemblies, but the electronic and the photonic properties of such hybrid nanoclusters remain difficult to predict and optimize. Here, split‐green fluorescence protein (sGFP) fragments are used as molecular glue and the GFP chromophore is used as a Raman reporter to assemble a variety of gold nanoparticle (AuNP) clusters and explore their plasmonic properties by numerical modeling. It is shown that GFP seeding of plasmonic nanogaps in AuNP/GFP hybrid nanoclusters increases near‐field dipolar couplings between AuNPs and provides SERS enhancement factors above 10⁸. Among the different nanoclusters studied, AuNP/GFP chains allow near‐infrared SERS detection of the GFP chromophore imidazolinone/exocyclic C?C vibrational mode with theoretical enhancement factors of 10⁸–10⁹. For larger AuNP/GFP assemblies, the presence of non‐GFP seeded nanogaps between tightly packed nanoparticles reduces near‐field enhancements at Raman active hot spots, indicating that excessive clustering can decrease SERS amplifications. This study provides rationales to optimize the controlled assembly of hot spot SERS nanoprobes for remote biosensing using Raman reporters that act as molecular glue between plasmonic nanoparticles.     

Size exclusion chromatography for semipreparative scale separation of Au38(SR)24 and Au40(SR)24 and larger clusters

Size exclusion chromatography (SEC) on a semipreparative scale (10 mg and more) was used to size-select ultrasmall gold nanoclusters (<2 nm) from polydisperse mixtures. In particular, the ubiquitous byproducts of the etching process toward Au(38)(SR)(24) (SR, thiolate) clusters were separated and gained in high monodispersity (based on mass spectrometry). The isolated fractions were characterized by UV-vis spectroscopy, MALDI mass spectrometry, HPLC, and electron microscopy. Most notably, the separation of Au(38)(SR)(24) and Au(40)(SR)(24) clusters is demonstrated.     

Synthesis of Branched DNA Scaffolded Super‐Nanoclusters with Enhanced Antibacterial Performance

Metal nanoclusters (NCs) possess unique optical properties, and exhibit a wide variety of potential applications. DNA with robust molecular programmability is demonstrated as an ideal scaffold to regulate the formation of NCs, offering a rational approach to precisely tune the spatial structures of NCs. Herein, the first use of branched DNA as scaffold to regulate the formation of silver nanoclusters (super‐AgNC) is reported, in which the spatial structures are precisely designed and constructed. Super‐AgNC with tunable shapes and arm‐lengths including Y‐, X‐, and (Y–X)‐ shaped super‐AgNC is achieved. The molecular structures and optical properties of super‐AgNCs are systemically studied. As a proof of application, remarkably, super‐AgNCs exhibit superior antibacterial performance. In addition, super‐AgNCs show excellent biocompatibility with three types of tissue cells including 293T (human embryonic kidney cells), SMCs (vascular smooth muscle cells), and GLC‐82 (lung adenocarcinoma cells). These performances enable the super‐AgNCs adaptable in a variety of applications such as biosensing, bioimaging, and antibacterial agents.     

Preparation and properties of gold nanoparticle-electrodeposited titanium substrates with Arg-Gly-Asp-Cys peptides

Titanium metal has good biocompatibility, superior mechanical properties and excellent corrosion resistance. Like most metals, however, it exhibits poor bioactive properties and fails to bond to bone tissue. To improve its bioactivity, bioactive molecules, such as peptides, can be grafted onto titanium surfaces. In order to do this, the first step may be to establish a stable and compatible linking layer on the titanium surface. In this study, we used electrochemical methods to deposit gold (Au) nanoparticles onto titanium substrates, to which we then grafted arginine-glycine-asparagine-cysteine (RGDC) peptides by thiolate covalent coupling. Properties of electrodeposited Au nanoparticles were evaluated using a variety of techniques, including microstructural, chemical and electrochemical measurements. The biological responses of the RGDC-grafted Ti substrates were evaluated using MG3 human osteoblast-like cells. The results of thin-film X-ray diffraction (TFXRD) and scanning electron microscopy (SEM) indicated the polycrystalline orientation of Au nanoparticles deposited on the titanium surfaces with high density and controllable particle size. The RGDC peptide could be covalently bonded to Au-deposited Ti substrates via Au-thiolate species, as expected. Cell morphology showed that, on RGDC-immobilized titanium with Au particles, MG63 cells attached and spread more rapidly than on Ti substrates either without peptide or with direct loading of the peptide. Immunostaining for focal adhesion kinase (FAK) demonstrated that RGDC enhanced cell attachment. The present method for the formation of Au nanoparticles may serve as an alternative route for bioactive molecule immobilization on Ti implants.     

Dual‐Functional Alginic Acid Hybrid Nanospheres for Cell Imaging and Drug Delivery

An effective and facile approach to prepare gold‐nanoparticle‐encapsulated alginic acid‐poly[2‐(diethylamino)ethyl methacrylate] monodisperse hybrid nanospheres (ALG–PDEA–Au) is developed by using monodisperse ALG–PDEA nanospheres as a precursor nanoparticulate reaction system. This approach utilizes particle‐interior chemistry, which avoids additional reductant or laborious separation process and, moreover, elegantly ensures that all the gold nanoparticles are located inside the hybrid nanospheres and every nanosphere is loaded with gold nanoparticles. These obtained ALG–PDEA–Au hybrid nanospheres have not only uniform size, similar surface properties, and good biocompatibility but also unique optical properties provided by the embedded gold nanoparticles. It is demonstrated that negatively charged ALG–PDEA–Au hybrid nanospheres can be internalized by human colorectal LoVo cancer cells and hence act as novel optical‐contrast reagents in tumor‐cell imaging by optical microscopy. Moreover, these hybrid nanospheres can also serve as biocompatible carriers for the loading and delivery of an anti‐cancer drug doxorubicin. In vitro cell viability tests reveal that drug‐loaded ALG–PDEA–Au hybrid nanospheres exhibit similar tumor cell inhibition to the free drug doxorubicin. Therefore, the obtained hybrid nanospheres successfully combine two functions, that is, cell imaging and drug delivery, into one single system, and may be of great application potential in other biomedical‐related areas.     

Tuning the Doping Type and Level of Graphene with Different Gold Configurations

Au nanoparticles and films are deposited onto clean graphene surfaces to study the doping effect of different Au configurations. Micro‐Raman spectra show that both the doping type and level of graphene can be tuned by fine control of the Au deposition. The morphological structures of Au on graphene are imaged by transmission electron microscopy, which indicate a size‐dependent electrical characteristic: isolated Au nanoparticles produce n‐type doping of graphene, while continuous Au films produce p‐type doping. Accordingly, graphene field‐effect transistors are fabricated, with the in situ measurements suggesting the tunable conductivity type and level by contacting with different Au configurations. For interpreting the experimental observations, the first‐principles approach is used to simulate the interaction within graphene–Au systems. The results suggest that, different doping properties of Au–graphene systems are induced by the chemical interactions between graphene and the different Au configurations (isolated nanoparticle and continuous film).     

Three-dimensional chemical imaging of embedded nanoparticles using atom probe tomography

Analysis of nanoparticles is often challenging especially when they are embedded in a matrix. Hence, we have used laser-assisted atom probe tomography (APT) to analyze the Au nanoclusters synthesized in situ using ion-beam implantation in a single crystal MgO matrix. APT analysis along with scanning transmission electron microscopy and energy dispersive spectroscopy (STEM-EDX) indicated that the nanoparticles have an average size ~8-12 nm. While it is difficult to analyze the composition of individual nanoparticles using STEM, APT analysis can give three-dimensional compositions of the same. It was shown that the maximum Au concentration in the nanoparticles increases with increasing particle size, with a maximum Au concentration of up to 50%.     

A Highly Stretchable and Real‐Time Healable Supercapacitor

In addition to a high specific capacitance, a large stretchability and self‐healing properties are also essential to improve the practicality and reliability of supercapacitors in portable and wearable electronics. However, the integration of multiple functions into one device remains challenging. Here, the construction of a highly stretchable and real‐time omni‐healable supercapacitor is demonstrated by sandwiching the polypyrrole‐incorporated gold nanoparticle/carbon nanotube (CNT)/poly(acrylamide) (GCP@PPy) hydrogel electrodes with a CNT‐free GCP (GP) hydrogel as the electrolyte and chemically soldering an Ag nanowire film to the hydrogel electrode as the current collector. The newly developed dynamic metal‐thiolate (M‐SR, M = Au, Ag) bond‐induced integrated configuration, with an intrinsically powerful electrode and electrolyte, enables the assembled supercapacitor to deliver an areal capacitance of 885 mF cm^?2 and an energy density of 123 µWh cm^?2, which are among the highest‐reported values for stretchable supercapacitors. Notably, the device exhibits a superhigh stretching strain of 800%, rapid optical healing capability, and significant real‐time healability during the charge–discharge process. The exceptional performance combined with the facile assembly method confirms this multifunctional device as the best performer among all the flexible supercapacitors reported to date.     

Binary Nanoparticle Superlattices for Plasmonically Modulating Upconversion Luminescence

Engineering a facile and controllable approach to modulate the spectral properties of lanthanide‐doped upconversion nanoparticles (UCNPs) is always an ongoing challenge. Herein, long‐range ordered, distinct two‐dimensional (2D) binary nanoparticle superlattices (BNSLs) composed of NaREF₄:Yb/Er (RE = Y and Gd) UCNPs and plasmonic metallic nanoparticles (Au NPs), including AB, AB₃, and AB₁₃ lattices, are fabricated via a slow evaporation‐driven self‐assembly to achieve plasmonic modulation of upconversion luminescence (UCL). Optical measurements reveal that typical red–green UCL from UCNPs can be effectively modulated into reddish output in BNSLs, with a drastically shortened lifetime. Notably, for AB₃‐ and AB₁₃‐type BNSLs with more proximal Au NPs around each UCNP, modified UCL with fine‐structured spectral lineshape is observed. These differences could be interpreted by the interplay of collective plasmon resonance introduced by 2D periodic Au arrays and spectrally selective energy transfer between UCNPs and Au. Thus, fabricating UCNP‐Au BNSLs with desired lattice parameters and NP configurations could be a promising way to tailor the UCL through controlled plasmonic modulation.     

Bottom‐Up Single‐Electron Transistors

As the downscaling of conventional semiconductor electronics becomes more and more challenging, the interest in alternative material systems and fabrication methods is growing. A novel bottom‐up approach for the fabrication of high‐quality single‐electron transistors (SETs) that can easily be contacted electrically in a controllable manner is developed. This approach employs the self‐assembly of Au nanoparticles forming the SETs, and Au nanorods forming the leads to macroscopic electrodes, thus bridging the gap between the nano‐ and microscale. Low‐temperature electron‐transport measurements reveal exemplary single‐electron tunneling characteristics. SET behavior can be significantly changed, post‐fabrication, using molecular exchange of the tunnel barriers, demonstrating the tunability of the assemblies. These results form a promising proof of principle for the versatility of bottom‐up nanoelectronics, and toward controlled fabrication of nanoelectronic devices.     

Assembly and interaction of Au/C core-shell nanostructures: in situ observation in the transmission electron microscope

Using transmission electron microscopy, we identify the temperature-dependent interaction pathway of carbon-supported Au nanoparticles. At low temperature (room temp. to 400 degrees C), Au nanoparticles predominantly interact by coalescence initiated by an atomic Au bridge. At high temperature (400-800 degrees C), the particles assemble into Au/C core-shell nanostructures. C-shells around individual nanoparticles passivate their surface and prevent coalescence. Ultimately coalescence does occur via rupture of the passivating shells, which invariably follows the assembly of C sheets enveloping and compressing multiple closely spaced Au/C nanoparticles.