Noble Metal Clusters: Applications in Energy,Environment, and Biology

Sub‐nanometer‐sized metal clusters, having dimensions between metal atoms and nanoparticles, have attracted tremendous attention in the recent past due to their unique physical and chemical properties. As properties of such materials depend strongly on size, development of synthetic routes that allows precise tuning of the cluster cores with high monodispersity and purity is an area of intense research. Such materials are also interesting owing to their wide variety of applications. Novel sensing strategies based on these materials are emerging. Owing to their extremely small size, low toxicity, and biocompatibility, they are widely studied for biomedical applications. Primary focus of this review is to provide an account of the recent advances in their applications in areas such as environment, energy, and biology. With further experimental and theoretical advances aimed at understanding their novel properties and solving challenges in their synthesis, an almost unlimited field of applications can be foreseen.     

Adsorption at cell surface and cellular uptake of silica nanoparticles with different surface chemical functionalizations: impact on cytotoxicity

Methods for the facile and in-line characterization of size distribution and physical properties of unsupported nanoparticles are of paramount importance for fundamental research and industrial applications. The state-of-the-art free nanoparticle characterization methods do not provide accuracy, high throughput, and operation easiness to support widespread use for routine characterization. In this perspective paper, we describe and discuss the opportunities provided by approaches for nanoparticle characterization based on optical measurements of the field scattered by particles. In particular, we show how insightful is the measure of both the real and the imaginary parts of the field amplitude, a task that has been considered in the past but never had a widespread exploitation. A number of opportunities are generated by this approach, in view of assessing a more efficient characterization and a better understanding of the properties of nanoparticles. We focus our attention on the capability of characterizing nanoparticles of wide interest for applications, considering cases where traditional approaches are not currently effective. Possible exploitations are both in research and in industrial environments: to validate a synthetic process, for example, or for in-line monitoring of a production plant to generate advanced process control tools, as well as decision-making tools for acting in real time during the production.     

Imaging the Hydrated Microbe‐Metal Interface Using Nanoscale Spectrum Imaging

PdAu nanocrystals are synthesised by Geobacter sulfurreducens, a dissimilatory metal‐reducing bacterium, and the resulting bimetallic nanocrystal‐decorated microbes are imaged using a range of advanced electron microscopy techniques. Specifically, the first example of elemental mapping of fully hydrated biological nanostructures using scanning transmission electron microscope (STEM) energy dispersive X‐ray (EDX) spectrum imaging within an environmental liquid‐cell is reported. These results are combined with cryo‐TEM and ex situ STEM imaging and EDX analysis with the aim of better understanding microbial synthesis of bimetallic nanoparticles. It is demonstrated that although Au and Pd are colocalized across the cells, the population of nanoparticles produced is bimodal, containing ultrasmall alloyed nanocrystals with diameters <3 nm and significantly larger core‐shell structures (>200 nm in diameter) which show higher Pd contents and exhibit a Pd enriched shell only a few nanometers thick. The application of high‐resolution imaging techniques described here offers the potential to visualize the microbe‐metal interface during the bioproduction of a range of functional materials by microbial “green” synthesis routes, and also key interfaces underpinning globally relevant environmental processes (e.g., metal cycling).     

Survey of Plasmonic Nanoparticles: From Synthesis to Application

The unique properties of plasmonic nanostructures have fuelled research based on the tremendous amount of potential applications. Their tailor‐made assemblies in combination with the tunable size and morphology of the initial building blocks allow for the creation of materials with a desired optical response. In this respect, it is crucial to synthesize nanoparticles with a defined shape that are at the core of such developments. Moreover, the interaction of individual nanoparticles with an incident electromagnetic field cannot only be influenced by their structure, but in fact, also by their spatial arrangement to each other. To harvest such opportunities, a profound theoretical understanding of these interactions is required as well as concise strategies to create such ordered assemblies. A quantitative evaluation of their optical properties can only be conducted when discrete structures of high uniformity can be achieved. As a consequence, separation steps have to be applied in order to obtain materials of high purity and uniformity. This also allows for an easier structural characterization of the nanoparticles and their assembled superstructures. In this progress report, an overview about the current development in this field of research is provided.     

Hydrogen generation from photoelectrochemical water splitting based on nanomaterials

Hydrogen is potentially one of the most attractive and environmentally friendly fuels for energy applications. Safe and efficient generation, storage, and utilization of hydrogen present major challenges in its widespread use. Hydrogen generation from water splitting represents a holy grail in energy science and technology, as water is the most abundant hydrogen source on the Earth. Among different methods, hydrogen generation from photoelectrochemical (PEC) water splitting using semiconductors as photoelectrodes is one of the most scalable and cost‐effective approaches. Compared to bulk materials, nanostructured semiconductors offer potential advantages in PEC application due to their large surface area and size‐dependent properties, such as increased absorption coefficient, increased band‐gap energy, and reduced carrier‐scattering rate. This article provides a brief overview of some recent research activities in the area of hydrogen generation from PEC water splitting based on nanostructured semiconductor materials, with a particular emphasis on metal oxides. Both scientific and technical issues are critically analyzed and reviewed.     

Internal Structure and Magnetic Properties in Cobalt Ferrite Nanoparticles: Influence of the Synthesis Method

The design of novel nanostructured magnetic materials requires a good understanding of the variation in the magnetic properties due to different synthesis conditions. In this work, four different procedures for fabricating Co‐ferrite nanoparticles with similar sizes between 7 and 10 nm are compared by studying their structural and magnetic properties. Non‐aqueous methods based on the thermal decomposition of metal acetylacetonates at high temperatures, either with or without surfactants, provide highly crystalline nanoparticles with large saturation magnetization values and a coherent reversal of the magnetic moment. However, variations in the density of defects and in the shape of the nanocrystals determine the distribution of switching fields and the effective magnetic anisotropy, which reaches up to ≈1 × 10⁷ erg cm^?3 for oleic acid‐capped 9 nm nanoparticles. It is shown that the saturation magnetization values for nanoparticles produced by different methods are in the range between 49 and 95 emu g^?1 due to differences in the stoichiometry, in the cation occupancy, in the magnetic disorder and in the spin canting of the magnetic sub‐lattices, the latter evaluated by in‐field Mössbauer spectroscopy.     

Monodispersed Bioactive Glass Nanoparticles Enhance the Osteogenic Differentiation of Adipose‐Derived Stem Cells through Activating TGF‐Beta/Smad3 Signaling Pathway

It is important to understand the interaction mechanisms between nanomaterials and adipose‐derived stem cells for biomedical application. Nanoscale bioactive glass has positive effects on guiding osteoblasts differentiation and bone regeneration. However, the effects and molecular mechanism of monodispersed bioactive glass nanoparticles on the osteogenic differentiation of adipose‐derived stem cells are still not clear up to now. In this study, the effects and underlying molecular mechanism of monodispersed bioactive glass nanoparticles on the osteogenic differentiation of adipose‐derived stem cells are investigated in minute detail. The results show that nanoparticles (100–200 nm) can be absorbed by stem cells and is distributed in cytoplasm and nucleus. In both culture conditions (normal and osteoinductive), nanoparticles (80 µg mL⁻¹) can significantly enhance the osteogenic differentiation of stem cells through upregulating the alkaline phosphatase activity, osteogenic genes and protein expressions, as well as calcium deposition. Further study suggests that the activation of transforming growth factor‐beta/Smad3 signaling pathway plays an important role in the osteogenic differentiation of adipose‐derived stem cells enhanced by monodispersed nanoparticles. This study may have important implications for better understanding of stem cells fate induced by monodispersed nanoparticles and provide a promising approach toward stem cells‐based bone regeneration.     

Scanning tunneling microscopy/spectroscopy on Au nanoparticles assembled using lauryl amine (LAM) and octadecane thiol (ODT)

In this report, we demonstrate scanning tunneling microscopy and spectroscopy on thin films of lauryl amine (LAM) and octadecane thiol (ODT) protected gold nanoparticles. We show that the zero current in the I-V curves (measure of Coulomb blockade (CB) of the nanoparticles) depends on the properties of the spacer molecule. In both the cases the gap voltage and the tunneling current at which the images are obtained are quite different which is further confirmed from the fitting performed based on the orthodox theory. The values for the capacitance and charging energy obtained from the fitting for ODT capped particles are comparable to the values obtained using spherical capacitor model. In contrast, values of these parameters were found to differ for LAM capped nanoparticles. While imaging, ODT capped nanoparticles were observed to drag along the scan direction leading to ordering of particles. Images of LAM capped gold nanoparticles show local ordering in self-assembly of particles although no evidence of large scale ordering in spatial Fourier transform was seen. These observations suggest that nanoparticles with larger CB would be imaged nonevasively in contrast to small CB systems for which tip induced effects will be dominant. In both the systems the current was found to rise faster than theoretical curves based on the orthodox theory suggesting that mechanism of charge transfer in this case may involve field emission rather than tunneling through a rectangular barrier. An attempt has been made to explain charge transfer based on Fowler-Nordheim (F-N) plots of the I-V curves.     

Probing Ag nanoparticle surface oxidation in contact with (in)organics: an X‐ray scattering and fluorescence yield approach

Characterizing interfacial reactions is a crucial part of understanding the behavior of nanoparticles in nature and for unlocking their functional potential. Here, an advanced nanostructure characterization approach to study the corrosion processes of silver nanoparticles (Ag‐Nps), currently the most highly produced nanoparticle for nanotechnology, is presented. Corrosion of Ag‐Nps under aqueous conditions, in particular in the presence of organic matter and halide species common to many natural environments, is of particular importance because the release of toxic Ag⁺ from oxidation/dissolution of Ag‐Nps may strongly impact ecosystems. In this context, Ag‐Nps capped with polyvinolpyrrolidone (PVP) in contact with a simple proxy of organic matter in natural waters [polyacrylic acid (PAA) and Cl^? in solution] has been investigated. A combination of synchrotron‐based X‐ray standing‐wave fluorescence yield‐ and X‐ray diffraction‐based experiments on a sample consisting of an approximately single‐particle layer of Ag‐Nps deposited on a silicon substrate and coated by a thin film of PAA containing Cl revealed the formation of a stable AgCl corrosion product despite the presence of potential surface stabilizers (PVP and PAA). Diffusion and precipitation processes at the Ag‐Nps–PAA interface were characterized with a high spatial resolution using this new approach.     

A bibliometric analysis of the development of next generation active nanotechnologies

Delineating the emergence of nanotechnologies that offer new functionalities is an important element in an anticipatory approach to the governance of nanotechnology and its potential impacts. This paper examines the transition to next generation active nanotechnologies which incorporate functions that respond to the environment or systems concepts that combine devices and structures that are dynamic and which may change their states in use. We develop an approach to identifying these active nanotechnologies and then use bibliometric analysis to examine the extent of research papers and patents involving these concepts. We also examine references to environmental, health, and safety concepts in these papers, given that these next generation nanotechnologies are likely to have risk profiles that are different from those of first-generation passive nanomaterials. Our results show a steady growth overall in focus on active nanotechnologies in the research literature and in patents over the study period of 1990–2010. We also find an increase in consideration given to environmental, health, and safety topics. While gaps are highlighted in our understanding of research and innovation in active nanotechnologies, the results suggest that there is beginning to be a shift to active nanotechnologies, with the implication that governance processes need to be conscious of this shift and to prepare for it.     

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.     

Self‐assembled silver nanoparticle monolayer on glassy carbon: an approach to SERS substrate

In this paper, the fabrication of an active surface‐enhanced Raman scattering (SERS) substrate by self‐assembled silver nanoparticles on a monolayer of 4‐aminophenyl‐group‐modified glassy carbon (GC) is reported. Silver nanoparticles are attached to the substrate through the electrostatic force between the negatively charged silver nanoparticles and the positively charged 4‐aminophenyl groups on GC. The active SERS substrate has been characterized by means of tapping‐mode atomic force microscopy (AFM), indicating that large quantities of silver nanoparticles are uniformly coated on the substrate. Rhodamine 6G (R6G) and p‐aminothiophenol (p‐ATP) are used as the probe molecules for SERS, resulting in high sensitivity to the SERS response, with the detection limit reaching as low as 10⁻⁹ M . This approach is easily controlled and reproducible, and more importantly, can extend the range of usable substrates to carbon‐based materials for SERS with high sensitivity. Copyright © 2007 John Wiley & Sons, Ltd.     

Lock‐In Thermography to Analyze Plasmonic Nanoparticle Dispersions

The physicochemical properties of nanoparticles (NPs) strongly rely on their colloidal stability, and any given dispersion can display remarkably different features, depending on whether it contains single particles or clusters. Thus, developing efficient experimental methods that are able to provide accurate and reproducible measures of the NP properties is a considerable challenge for both research and industrial development. By analyzing different NPs, through size and concentration, it is demonstrated that lock‐in thermography, based on light absorption and heat generation, is able to detect and differentiate the distinct aggregation and re‐dispersion behavior of plasmonic NPs, e.g., gold and silver. Most importantly, the approach is nonintrusive and potentially highly cost‐effective compared to standard analytical techniques.     

In Situ Synchrotron X‐Ray Techniques for Real‐Time Probing of Colloidal Nanoparticle Synthesis

Solution‐phase synthesis of colloidal nanoparticles with precisely tailored properties is one of the fastest growing research topic and represents the most critical foundation to implant nanotechnology in a variety of areas to boost performance of traditional systems. Comprehensive understanding of the nucleation and growth mechanisms involved in the formation of colloidal nanoparticles is very important to realize rational design and synthesis of well‐tailored nanoparticles and requires appropriate in situ techniques to probe the kinetics of the synthetic reactions. Synchrotron hard X‐rays represent a class of promising probes for solution‐phase reactions due to their strong penetration in ambient environment and solutions. This review completely summarizes the in situ synchrotron X‐ray techniques emerged in the recent years for real‐time probing nanophase evolution of colloidal nanoparticles. Typical examples of colloidal nanoparticle syntheses are discussed in detail to shed the light on the advantages and disadvantages of individual techniques.     

Shape‐Tunable Selective Synthesis of Bismuth Fluoride Nanostructures for Versatile Applications

A facile approach for shape‐tunable synthesis of bismuth fluoride nanoparticles is reported. The approach is based on the homogeneous precipitation of precursor materials in mixed solvents (H₂O and ethylene glycol) and only ethylene glycol. The influencing factors on the morphology of the particles, i.e., solvent ratio, F/Bi ratio, and ethylenediaminetetraacetic acid, are studied in detail, and are schematically illustrated. The morphology, crystallinity, structure, and optical properties of the prepared samples are characterized by using a field‐emission scanning electron microscope, transmission electron microscope, X‐ray diffractometer, Fourier transform infrared spectrometer, and spectrofluorometer, respectively. The hollow sphere‐shaped nanoparticle doped with Eu³⁺ ions exhibit reddish orange emission under ultraviolet illumination due to the symmetric environment around the dopant ions. Subsequently, the effect of dopant concentration on the optical properties is also evaluated. The temperature‐dependent photoluminescence emission spectra reveal good thermal stability. The obtained results provide an efficient strategy for synthesizing the shape‐tunable nanoparticles with excellent optical properties.     

基于金纳米粒子的光谱分析法进行单细胞探测

在过去的几十年中,等离子纳米粒子,尤其是金纳米粒子(AuNPs),由于其独特的局部表面等离子体共振(LSPR)特性,金纳米颗粒非常适合高度传导定域在表面的化学或物理刺激产生的光信号,已被广泛应用于生物检测与成像。包括单细胞光谱分析与成像。基于光吸收和弹性光学方法散射,阐述了利用光谱方法进行的单细胞光学探测的进展应用和纳米系统表现出新的特性。论述了基于AuNPs的细胞内环境光谱分析与探测,对在单细胞水平上进行的细胞动态实时测量的基本原则和与光互动独特的相关方法进行了描述。重点放在单细胞光谱检测的原则、方法及这些方法的优点和挑战,并阐述了最近在这一领域的研究进展,内容包括细胞和亚细胞环境的探测、细胞应答诱导细胞凋亡过程探测、生物分子识别和量化、药物传递及释放、癌症诊断及治疗等。给出了未来的挑战和努力方向。     

Iron Precursor Decomposition in the Magnesium Combustion Flame: A New Approach for the Synthesis of Particulate Metal Oxide Nanocomposites

Powders of Fe–Mg–O nanocomposite particles have been grown using a novel chemical vapor synthesis approach that employs the decomposition of a metalorganic precursor inside the metal combustion flame. After annealing in controlled gas atmospheres composition distribution functions, structure and phase stability of the obtained magnesiowüstite nanoparticles are measured with a combination of techniques such as inductively coupled plasma‐optical emission spectroscopy, energy dispersive X‐ray spectroscopy, X‐ray diffraction, and scanning and transmission electron microscopy. Complementary Mössbauer spectroscopy measurements reveal that depending on Fe loading and temperature of annealing either metastable and superparamagnetic solid solutions of Fe³⁺ ions in periclase (MgO) or phase separated mixtures of MgO and ferrimagnetic magnesioferrite (MgFe₂O₄) nanoparticles can be obtained. The described combustion technique represents a novel concept for the production of mixed metal oxide nanoparticles. Adressing the impact of selected annealing protocols, this study underlines the great potential of vapor phase grown non‐equilibrium solids, where thermal processing provides means to trigger phase separation and, concomitantly, the emergence of new magnetic properties.     

Utilizing broadband X‐rays in a Bragg coherent X‐ray diffraction imaging experiment

A method is presented to simplify Bragg coherent X‐ray diffraction imaging studies of complex heterogeneous crystalline materials with a two‐stage screening/imaging process that utilizes polychromatic and monochromatic coherent X‐rays and is compatible with in situ sample environments. Coherent white‐beam diffraction is used to identify an individual crystal particle or grain that displays desired properties within a larger population. A three‐dimensional reciprocal‐space map suitable for diffraction imaging is then measured for the Bragg peak of interest using a monochromatic beam energy scan that requires no sample motion, thus simplifying in situ chamber design. This approach was demonstrated with Au nanoparticles and will enable, for example, individual grains in a polycrystalline material of specific orientation to be selected, then imaged in three dimensions while under load.     

Silica Nanoparticles as Adhesives for Biological Tissues? Re‐Examining the Effect of Particles Size,Particle Shape,and the Unexpected Role of Base

Development of new, effective, and patient‐friendly adhesives for biological tissues is important for medical and surgical practices such as bleeding control and organ repairing. While some commercially available silica nanoparticles such as LUDOX SM‐30 have shown adhesive properties for biological tissues, the role of inorganic base present in the adhesive properties of the silica nanoparticles has not been examined. Moreover, it remained unclear how the size and the shape of silica nanoparticles affect the adhesion properties. To address these questions, synthesis and characterization of a series of uniform silica nanostructures with different sizes and shapes is carried out. Unexpectedly, none of the synthesized silica nanostructures without additional inorganic base shows adhesion properties against liver tissues. Such surprising phenomena motivate to examine other factors in the commercial silica nanoparticles as tissue adhesives, and reach a conclusion that the inorganic base plays a key role in the adhesion properties. It is believed that this study answers the important question whether silica nanoparticles can act as biological adhesives or not. The conclusion also gives a lesson to other scientists and engineers in design and exploration of new biological adhesives.     

Intramolecular charge transfer in donor‐bridge‐acceptor compounds with paired linearly conjugated or cross‐conjugated pathways

An understanding of intramolecular charge transfer in 2‐D linearly conjugated and cross‐conjugated compounds is necessary for the rational design of molecular electronics, improved solar energy devices, semi‐conducting polymers, and materials with nonlinear optical properties. In this work, the femtosecond transient absorption spectra and kinetics of several donor‐bridge‐acceptor compounds containing cross‐conjugated or linearly conjugated bridging groups were obtained. The veratrole group was used as the donor, and the phthalimide group was used as an acceptor. 2‐D conjugation was achieved by involving two bridging groups arranged cyclically between the donor and acceptor. The donor and acceptor were bridged by m‐phenylene in the cross‐conjugated compounds or 2,5‐thiophene in the linearly conjugated compounds. We found slower charge separation times and slower charge recombination times in the compounds containing cyclic cross‐conjugated bridging groups than in those containing the cyclic linearly conjugated groups in polar solvent. Charge separation rates that were found to be dependent on solvent were observed in the donor‐bridge‐acceptor compounds. Copyright © 2014 John Wiley & Sons, Ltd.