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.     

Near‐field optical enhancement by lead‐sulfide quantum dots and metallic nanoparticles for SERS

There is a growing interest in using quantum dots (QDs) and metallic nanoparticles (NPs), both for luminescence enhancement and surface‐enhanced Raman scattering (SERS). Here, we study the electromagnetic‐field enhancement that can be generated by lead‐sulfide (PbS) QDs using three‐dimensional finite‐element simulations. We investigate the field enhancement associated with combinations of PbS QDs with metallic NPs and substrates. The results show that high field enhancement can be achieved by combining PbS QDs with metallic NPs of larger sizes. The ideal size for Ag NPs is 25 nm, providing a SERS enhancement factor of ~5*10⁸ for light polarization parallel to the NP dimer axis and a gap of 0.6 nm. For Au NPs, the bigger the size, the higher is the field for the studied diameters, up to 50 nm. The near‐field values for PbS QDs above metallic substrates were found to be lower compared to the case of PbS QD‐metal NP dimers. This study provides the understanding for the design and application of QDs for the enhancement of near‐field phenomena. Copyright © 2013 John Wiley & Sons, Ltd.     

Radiobiological Implications of Nanoparticles Following Radiation Treatment

Materials with a high atomic number (Z) are shown to cause an increase in the level of cell kill by ionizing radiation when introduced into tumor cells. This study uses in vitro experiments to investigate the differences in radiosensitization between two cell lines (MCF-7 and U87) and three commercially available nanoparticles (gold, gadolinium, and iron oxide) irradiated by 6 MV X-rays. To assess cell survival, clonogenic assays are carried out for all variables considered, with a concentration of 0.5 mg mL⁻¹ for each nanoparticle material used. This study demonstrates differences in cell survival between nanoparticles and cell line. U87 shows the greatest enhancement with gadolinium nanoparticles (2.02 ± 0.36), whereas MCF-7 cells have higher enhancement with gold nanoparticles (1.74 ± 0.08). Mass spectrometry, however, shows highest elemental uptake with iron oxide and U87 cells with 4.95 ± 0.82 pg of iron oxide per cell. A complex relationship between cellular elemental uptake is demonstrated, highlighting an inverse correlation with the enhancement, but a positive relation with DNA damage when comparing the same nanoparticle between the two cell lines.     

Nanosized Particles of Tantalum,Hafnium, and Cerium Oxides Used with Monochromatic Photon Beams and Brachytherapy Sources

High-Z nanoparticles can increase the absorbed radiation dose if they are accumulated in tumor cells. The quantitative measure of this radiosensitization effect is the dose enhancement factor (DEF), that is, the ratio of the doses absorbed in the presence and in the absence of nanoparticles. In the present work, the values of the dose enhancement factors of Ta₂O₅, HfO₂, and CeO₂ ceramic nanoparticles were calculated analytically for monochromatic radiation of the X-ray energy range (1–180 keV) and for low-energy sources for brachytherapy: ¹⁰³Pd (mean energy, 20.6 keV), ¹²⁵I (26.7 keV), and ¹³¹Cs (30.4 keV). For all types of nanoparticles in the concentration of 5 mg/mL, the values of the dose enhancement factor were high both for monochromatic radiation and for brachytherapy sources. The highest DEF values of ~1.7 were obtained for nanoparticles of tantalum oxide. For brachytherapy sources, the highest dose enhancement factors (1.48 to 1.67) were obtained for Ta₂O₅ and HfO₂ nanoparticles. These results confirm that ceramic nanoparticles are promising dose modifying agents for radiotherapy.     

A hybrid substrate for surface‐enhanced Raman scattering spectroscopy: coupling metal nanoparticles to strong localised fields on a micro‐structured surface

Electromagnetic coupling between localised plasmons on metal nanoparticles and the strong localised fields on a micro‐structured surface is demonstrated as a means to increase the enhancement factor in surface‐enhanced Raman scattering (SERS) spectroscopy. Au nanoparticles of diameter 20 nm were deposited on a micro‐structured Au surface consisting of a periodic array of square‐based pyramidal pits (Klarite). The spectra of 4‐aminothiophenol (4‐ATP) were compared before and after deposition of Au nanoparticles on the micro‐structured surface. The addition of Au nanoparticles is shown to provide significantly higher signal intensities, with improvements of the order of ∼10³ per molecule compared with spectra obtained from the micro‐structured substrate alone. This hybrid approach offers promise for combining nanoparticles with micro‐ and nano‐structured surfaces in order to design SERS substrates with higher sensitivities. Copyright © 2011 John Wiley & Sons, Ltd.     

Single‐cell resolution in high‐resolution synchrotron X‐ray CT imaging with gold nanoparticles

Gold nanoparticles are excellent intracellular markers in X‐ray imaging. Having shown previously the suitability of gold nanoparticles to detect small groups of cells with the synchrotron‐based computed tomography (CT) technique both ex vivo and in vivo, it is now demonstrated that even single‐cell resolution can be obtained in the brain at least ex vivo. Working in a small animal model of malignant brain tumour, the image quality obtained with different imaging modalities was compared. To generate the brain tumour, 1 × 10⁵ C6 glioma cells were loaded with gold nanoparticles and implanted in the right cerebral hemisphere of an adult rat. Raw data were acquired with absorption X‐ray CT followed by a local tomography technique based on synchrotron X‐ray absorption yielding single‐cell resolution. The reconstructed synchrotron X‐ray images were compared with images obtained by small animal magnetic resonance imaging. The presence of gold nanoparticles in the tumour tissue was verified in histological sections.     

Intracerebral delivery of 5‐iodo‐2′‐deoxyuridine in combination with synchrotron stereotactic radiation for the therapy of the F98 glioma

Iodine‐enhanced synchrotron stereotactic radiotherapy takes advantage of the radiation dose‐enhancement produced by high‐Z elements when irradiated with mono‐energetic beams of synchrotron X‐rays. In this study it has been investigated whether therapeutic efficacy could be improved using a thymidine analogue, 5‐iodo‐2′‐deoxyuridine (IUdR), as a radiosentizing agent. IUdR was administered intracerebrally over six days to F98 glioma‐bearing rats using Alzet osmotic pumps, beginning seven days after tumor implantation. On the 14th day, a single 15 Gy dose of 50 keV synchrotron X‐rays was delivered to the brain. Animals were followed until the time of death and the primary endpoints of this study were the mean and median survival times. The median survival times for irradiation alone, chemotherapy alone or their combination were 44, 32 and 46 days, respectively, compared with 24 days for untreated controls. Each treatment alone significantly increased the rats' survival in comparison with the untreated group. Their combination did not, however, significantly improve survival compared with that of X‐irradiation alone or chemotherapy alone. Further studies are required to understand why the combination of chemoradiotherapy was no more effective than X‐irradiation alone.     

Single‐Cell Investigations of Silver Nanoparticle–Bacteria Interactions

Interaction of bacteria with citrate‐reduced silver nanoparticles (AgNPs) of size 25 nm ± 8.5 nm is studied using Raman spectroscopy in conjunction with plasmon resonance imaging of single bacterial cells. Distribution of isolated nanoparticles (NPs) inside Escherichia coli (ATCC 25922; E. coli) is observed by hyperspectral imaging (HSI) as a function of incubation time. Time‐dependent degradation of bacterial DNA upon incubation of AgNPs with E. coli is proven by Raman spectroscopic studies. While attachment of NPs is evident in HSI, molecular changes are evident from the surface‐enhanced Raman spectra of adsorbed DNA and its fragments. Distinct enhancement of DNA features is observed upon interaction of AgNPs and the number of such distinct features increases with incubation time, reaches a maximum, and decreases afterwards. This systematic interaction of DNA with the NPs system and its gradual chemical evolution is proven by investigating isolated plasmid DNA. A comparative Raman study with silver ions has shown that DNA features are observable only when bacteria are incubated with AgNPs. Energetics of interaction examined with microcalorimetry suggests the exothermicity of ?1.547 × 10¹⁰ cal mol^?1 for the NP–bacteria system. Specific interaction of AgNPs with exocyclic nitrogen present in the bases, adenine, guanine, and cytosine, leads to the changes in DNA.     

A facile high‐performance SERS substrate based on broadband near‐perfect optical absorption

Plasmonic systems based on metal nanoparticles on a metal film with high optical absorption have generated great interests for surface‐enhanced Raman scattering (SERS). In this study, we prepare a broadband‐visible light absorber consisting Au nanotriangles on the surface of a continuous optically opaque gold film separated with a dielectric SiO₂ layer, which is a typical metal‐insulator‐metal (MIM) system, and demonstrate it as an efficient SERS substrate. The MIM nanostructure, prepared using nanosphere lithography with a very large area, shows a broadband with absorption exceeding 90% in the wavelength regime of 630–920 nm. We observe an average SERS enhancement factor (EF) as large as 4.9 × 10⁶ with a 22‐fold increase compared to a single layer of Au nanotriangles directly on a quartz substrate. A maximum SERS EF can be achieved by optimizing the thicknesses of the dielectric layer to control the optical absorption. Owing to the simple, productive, and inexpensive fabrication technique, our MIM nanostructure could be a potential candidate for SERS applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Gold‐coated zinc oxide nanowire‐based substrate for surface‐enhanced Raman spectroscopy

Zinc oxide nanowires with two distinct morphologies were synthesized on silicon substrates using a simple thermal evaporation and vapor transport method in an oxidizing environment. The as‐synthesized nanowires were coated with gold to allow excitation of surface plasmons over a broad frequency range. SERS studies with near‐IR excitation at 785 nm showed significant enhancement (average enhancement > 10⁶) with excellent reproducibility to detect monolayer concentrations of 4‐methylbenzenethiol (4‐MBT) and 1,2‐benzendithiol (1,2‐BDT) probe molecules. The Raman enhancement showed a strong dependence on the gold film thickness, and the peak enhancement was observed for a ∼40‐nm‐thick film. The Raman enhancement was stronger for randomly oriented nanowires compared to aligned ones suggesting the importance of contributions from the junctions of nanowires. Copyright © 2009 John Wiley & Sons, Ltd.     

Scattering Invisibility With Free‐Space Field Enhancement of All‐Dielectric Nanoparticles

Simultaneous scattering invisibility and free‐space field enhancement have been achieved based on multipolar interferences among all‐dielectric nanoparticles. The scattering properties of all‐dielectric nanowire quadrumers are investigated and two sorts of scattering invisibilities have been identified: the trivial invisibility where the individual nanowires are not effectively excited; and the nontrivial invisibility with strong multipolar excitations within each nanowire, which results in free‐space field enhancement outside the particles. It is revealed that such nontrivial invisibility originates from not only the simultaneous excitations of both electric and magnetic resonances, but also their significant magnetoelectric cross‐interactions. We further show that the invisibility obtained is both polarization and direction selective, which can probably play a significant role in various applications including non‐invasive detection, sensing, and non‐disturbing medical diagnosis with high sensitivity and precision.     

Distinguishing chemical and electromagnetic enhancement in surface‐enhanced Raman spectra: The case of para‐nitrothiophenol

Surface‐enhanced Raman spectra are simulated using a combined classical electrodynamics/real‐time time‐dependent density functional theory approach and compared to experiments. Emphasis is put on discerning between chemical and electromagnetic enhancement. Therefore, three different calculation scenarios are investigated using para‐nitrothiophenol as a test molecule. In the first one, corresponding to electromagnetic enhancement, we simulate the molecule alone with ab initio computations incorporating the electromagnetic field emitted by a nanoparticle. Chemical enhancement is modeled in the second scenario, where we include not only the molecule into the quantum chemistry calculations but also metal atoms of the nanoparticle. Here, any modification of the electromagnetic field due to the nanoparticle is not considered. In the third scenario, the former two setups are combined and demanding simulations of the hybrid system containing the molecule and the metal atoms exposed to a strongly modified electromagnetic field due to the plasmonic properties of the metallic nanoparticles are considered. Results are compared to our experimentally measured spectra. Based on our analysis, we show here on rigorous grounds that the electromagnetic effect leads to increased absolute Raman scattering cross sections but no change of the relative intensities. In contrast, the chemical effect leads to changes in relative peak height and also to newly emerging bands in the spectrum. These findings will have major implications in any study that concerns the interaction of molecules with metallic nanostructures. Copyright © 2013 John Wiley & Sons, Ltd.     

Particle‐Arrayed Silver Mesocubes Synthesized via Reducing Silver Oxide Mesocrystals for Surface‐Enhanced Raman Spectroscopy

In this study, we demonstrate an easy particle‐mediated protocol using the specific structure of mesocrystal Ag₂O sacrificial templates to synthesize highly rough‐cubic Ag mesocages. To the best of our knowledge, the mesocrystal particles are reported for the first time as sacrificial templates for synthesizing metal particles. The obtained Ag mesocages show high surface‐enhanced Raman scattering (SERS) sensitivity because of the highly rough topography formed by arrays of uniform individual Ag nanoparticles. Abundant “hot spots” with greatly enhanced local electromagnetic field are promoted densely on the mesocage surface by the plenty of deep and narrow gaps and the hollow structure. The single‐particle SERS signal generated by the Ag mesocage has an enhancement factor of approximately 10⁹, which is approximately four times higher than the Ag mesocage synthesized using single‐crystal Ag₂O particle as a template. Meanwhile, this signal displays a linear dependence on the detected analyte concentration, sensitively down to 1.0 × 10^?12 m .     

Fabrication of surface‐enhanced Raman scattering‐active ZnO/Ag composite microspheres

We show in this paper how zinc oxide (ZnO)/silver (Ag) composite microspheres can be prepared by the reduction of Ag(NH₃)₂⁺ with the reducing agent formaldehyde in aqueous solution on the surface of ZnO microspheres. During the preparation, Sn²⁺ was absorbed on the surface of ZnO microspheres for sensitization and activation, and then Ag(NH₃)₂⁺ was reduced to Ag nanoparticles by the reducing agent to obtain ZnO/Ag composite microspheres. SEM and TEM images revealed silver nanoparticles with a diameter ranging from tens to 100 nm. X‐Ray photoelectron spectra (XPS), X‐ray diffraction (XRD) patterns and UV‐vis spectra were used to characterize the structure of the ZnO/Ag composite microspheres. The origin of the surface‐enhanced Raman scattering properties was traced to the surface of the ZnO/Ag composite microspheres. The enhancement factor was estimated in detail, and the enhancement mechanism for the SERS effect was also investigated. Copyright © 2007 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering studies of carbon nanotubes using Ag‐core Au‐shell nanoparticles

Surface‐enhanced Raman scattering from carbon nanotube bundles adsorbed with plasmon‐tunable Ag‐core Au‐shell nanoparticles (Ag@Au nps) was carried out for the first time. By utilizing nanoparticles whose plasmon resonance peak (541, 642 nm) closely matches the commonly used Raman excitation sources (532, 632.81 nm), we can observe a large enhancement in the Raman signatures of carbon nanotubes. We obtain greater enhancement in the Raman signal for the above case when compared to nanotubes adsorbed with conventional Ag, Au or other ‘off resonant’ Ag@Au nps. The power‐dependent SERS experiment on single‐walled nanotubes (SWNTs) with resonant Ag@Au nps reveals a linear behavior between the G‐band intensity and the photon flux density, which is in agreement with the vibrational pumping model of SERS. The observed enhancement by resonance matching is pronounced for carbon nanotubes and may lead to insights into understanding nanotube–nanoparticle interaction. Copyright © 2009 John Wiley & Sons, Ltd.     

Improved performance of silicon‐nanoparticle film‐coated dye‐sensitized solar cells

Silicon (Si) nanoparticles with average size of 13 nm and orange–red luminescence under UV absorption were synthesized using electrochemical etching of silicon wafers. A film of Si nanoparticles with thickness of 0.75 µm to 2.6 µm was coated on the glass (TiO₂ side) of a dye‐sensitized solar cell (DSSC). The cell exhibited nearly 9% enhancement in power conversion efficiency (η) at film thickness of ～2.4 µm under solar irradiation of 100 mW/cm² (AM 1.5) with improved fill factor and short‐circuit current density. This study revealed for the first time that the Si‐nanoparticle film converting UV into visible light and helping in homogeneous irradiation, can be utilized for improving the efficiency of the DSSCs. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nuclear Uptake of Gold Nanoparticles Deduced Using Dual‐Angle X‐Ray Fluorescence Mapping

Studies into the cell nucleus' incorporation of gold nanoparticles (AuNPs) are often limited by ambiguities arising from conventional imaging techniques. Indeed, it is suggested that to date there is no unambiguous imaging evidence for such uptake in whole cells, particularly at the single nanoparticle level. This shortcoming in understanding exists despite the nucleus being the most important subcellular compartment in eukaryotes and gold being the most commonly used metal nanoparticle in medical applications. Here, dual‐angle X‐ray flouresence is used to show individually resolved nanoparticles within the cell nucleus, finding them to be well separated and 79% of the intranuclear population to be monodispersed. These findings have important implications for nanomedicine, illustrated here through a specific exemplar of the predicted enhancement of radiation effects arising from the observed AuNPs, finding intranuclear dose enhancements spanning nearly five orders of magnitude.     

Fabrication and characterization of SERS‐active silver clusters on glassy carbon

In this article, a novel technique for the fabrication of surface enhanced Raman scattering (SERS) active silver clusters on glassy carbon (GC) has been proposed. It was found that silver clusters could be formed on a layer of positively charged poly(diallyldimethylammonium) (PDDA) anchored to a carbon surface by 4‐aminobenzoic acid when a drop containing silver nanoparticles was deposited on it. The characteristics of the obtained silver clusters have been investigated by atomic force microscopy (AFM), SERS and an SERS‐based Raman mapping technique in the form of line scanning. The AFM image shows that the silver clusters consist of several silver nanoparticles and the size of the clusters is in the range 80–100 nm. The SERS spectra of different concentrations of rhodamine 6G (R6G) on the silver clusters were obtained and compared with those from a silver colloid. The apparent enhancement factor (AEF) was estimated to be as large as 3.1 × 10⁴ relative to silver colloid, which might have resulted from the presence of ‘hot‐spots’ at the silver clusters, providing a highly localized electromagnetic field for the large enhancement of the SERS spectra of R6G. The minimum electromagnetic enhancement factor (EEF) is estimated to be 5.4 × 10⁷ by comparison with the SERS spectra of R6G on the silver clusters and on the bare GC surface. SERS‐based Raman mapping technique in the form of line scanning further illustrates the good SERS activity and reproducibility on the silver clusters. Finally, 4‐mercaptopyridine (4‐Mpy) was chosen as an analyte and the lowest detected concentration was investigated by the SERS‐active silver clusters. A concentration of 1.6 × 10⁻¹⁰ M 4‐Mpy could be detected with the SERS‐active silver clusters, showing the great potential of the technique in practical applications of microanalysis with high sensitivity. Copyright © 2006 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering of silylated graphite oxide sheets sandwiched between colloidal silver nanoparticles and silver piece

Graphite oxide (GO) was successfully silylated by 3‐mercaptopropyltrimethoxysilane. The surface‐enhanced Raman scattering spectrum of the silylated GO sheets sandwiched between colloidal silver nanoparticles and silver piece is presented. The Raman signal shows a 10⁴ enhancement compared to that of bulk GO. The large Raman enhancement is most likely a result of electromagnetic (EM) coupling between the colloidal silver nanoparticles (localized surface plasmon) and the silver piece (surface plasmon polariton), creating large localized EM fields at their interface, where the silylated GO sheets reside in this sandwich architecture. Copyright © 2009 John Wiley & Sons, Ltd.     

The distributions of enhancement factors in close‐packed and nonclose‐packed surface‐enhanced Raman substrates

A method employing photochemical hole burning, previously developed to measure the distribution of Raman enhancement factors on a nanostructured substrate for surface‐enhanced Raman scattering, is used to compare the enhancement distributions of benzenethiol adsorbed on substrates optimized for 532 nm laser excitation consisting of close‐packed (CP) or nonclose‐packed (NCP) nanospheres. The ensemble‐averaged Raman enhancement factor was 2.8 times smaller for the NCP substrate. The measured distributions revealed additional information. For instance, 92% of the molecules on the CP substrate and 93.6% of the molecules on the NCP substrate had Raman enhancements below average. The minimum enhancements on both substrates were ~10⁴, but on the NCP substrate the maximum enhancement was 1.2 × 10⁸, whereas on the CP substrate the maximum was 2 × 10¹⁰. The Ag‐coated nanospheres form hemisphere‐on‐cylinder mushroom‐like structures on both lattices, but on the NCP lattice, one third of the molecules are on the flat regions between the mushrooms. The flats on the NCP lattice have enhancements of ~10⁴, showing they are part of a resonant plasmonic structure. The highest NCP enhancements of ~10⁸ are tentatively associated with regions at the bases of the mushrooms, whereas the highest CP enhancements of 2 × 10¹⁰ are tentatively associated with gaps between nanospheres where 0.0025% of the molecules reside. Copyright © 2011 John Wiley & Sons, Ltd.