Chemical sensing and imaging with metallic nanorods

In this Feature Article, we examine recent advances in chemical analyte detection and optical imaging applications using gold and silver nanoparticles, with a primary focus on our own work. Noble metal nanoparticles have exciting physical and chemical properties that are entirely different from the bulk. For chemical sensing and imaging, the optical properties of metallic nanoparticles provide a wide range of opportunities, all of which ultimately arise from the collective oscillations of conduction band electrons ("plasmons") in response to external electromagnetic radiation. Nanorods have multiple plasmon bands compared to nanospheres. We identify four optical sensing and imaging modalities for metallic nanoparticles: (1) aggregation-dependent shifts in plasmon frequency; (2) local refractive index-dependent shifts in plasmon frequency; (3) inelastic (surface-enhanced Raman) light scattering; and (4) elastic (Rayleigh) light scattering. The surface chemistry of the nanoparticles must be tunable to create chemical specificity, and is a key requirement for successful sensing and imaging platforms.     

A general synthetic strategy for oxide-supported metal nanoparticle catalysts

Despite recent exciting progress in catalysis by supported gold nanoparticles, there remains the formidable challenge of preparing supported gold catalysts that collectively incorporate precise control over factors such as size and size-distribution of the gold nanoparticles, homogeneous dispersion of the particles on the support, and the ability to utilize a wide range of supports that profoundly affect catalytic performance. Here, we describe a synthetic methodology that achieves these goals. In this strategy, weak interface interactions evenly deposit presynthesized organic-capped metal nanoparticles on oxide supports. The homogeneous dispersion of nanoparticles on oxides is then locked in place, without aggregation, through careful calcination. The approach takes advantage of recent advances in the synthesis of metal and oxide nanomaterials and helps to bring together these two classes of materials for catalysis applications. An important feature is that the strategy allows metal nanoparticles to be well dispersed on a variety of oxides with few restrictions on their physical and chemical properties. Following this synthetic procedure, we have successfully developed efficient gold catalysts for green chemistry processes, such as the production of ethyl acetate from the selective oxidation of ethanol by oxygen at 100 degrees C.     

金纳米粒子与蛋白质的相互作用及其应用

金纳米粒子与蛋白质间存在多种作用方式,包括物理吸附、化学共价结合以及非共价特异性吸附等.金纳米粒子表面等离子体共振效应引起可见光区的特征吸收及表面增强拉曼散射,常用来研究金纳米粒子与蛋白质间的相互作用.金纳米粒子与蛋白质间的作用与纳米粒子的尺寸、表面化学及蛋白质的大小、电荷、氨基酸残基有关.利用金纳米粒子与蛋白质的相互作用及纳米金的谱学性质,可以对疾病或环境污染进行简单、高效、低成本检测,也可用于疾病治疗.     

Catalytic activity of TiO2 nanoparticles in the synthesis of some 2,3-disubstituted dihydroquinazolin-4（1H）-ones

Green chemistry is playing an important role for synthesizing organic compounds, due to its eco-friendly nature and low cost. In green chemistry, metal nanoparticles exhibited some useful physical and chemical properties （catalytic activity）. Due to its diverse properties, nanoparticles can be utilized as a catalyst in various organic reactions. Recent research has been directed towards the utilization of eco- friendly and bio-friendly plant materials in nanoparticles synthesis. In our present work, TiO2 nanoparticles （TiO2 NPs） were synthesized using Annona squamosa peel extract and their catalytic applications were studied on the 2,3-disubstituted dihydroquinazolin-4（l1H）-one synthesis. Synthesized compounds were confirmed using FT-IR.1H NMR, 13C NMR and GC-MS analyses.     

Surface Faceting and Reconstruction of Ceria Nanoparticles

The surface atomic arrangement of metal oxides determines their physical and chemical properties, and the ability to control and optimize structural parameters is of crucial importance for many applications, in particular in heterogeneous catalysis and photocatalysis. Whereas the structures of macroscopic single crystals can be determined with established methods, for nanoparticles (NPs), this is a challenging task. Herein, we describe the use of CO as a probe molecule to determine the structure of the surfaces exposed by rod‐shaped ceria NPs. After calibrating the CO stretching frequencies using results obtained for different ceria single‐crystal surfaces, we found that the rod‐shaped NPs actually restructure and expose {111} nanofacets. This finding has important consequences for understanding the controversial surface chemistry of these catalytically highly active ceria NPs and paves the way for the predictive, rational design of catalytic materials at the nanoscale.     

Localized Template‐Driven Functionalization of Nanoparticles by Dynamic Combinatorial Chemistry

We have developed a method for the localized functionalization of gold nanoparticles using imine‐based dynamic combinatorial chemistry. By using DNA templates, amines were grafted on the aldehyde‐functionalized nanoparticles only if and where the nanoparticles interacted with the template molecules. Functionalization of the nanoparticles was controlled solely by the DNA template; only amines capable of interacting with DNA were bound to the surface. Interestingly, even though our libraries contained only a handful of simple amines, the DNA sequence influenced their attachment to the surface. Our method opens up new opportunities for the synthesis of multivalent, nanoparticle‐based receptors for biomacromolecules.     

Controlling ultrasmall gold nanoparticles with atomic precision

Gold nanoparticles are probably the nanoparticles that have been best studied for the longest time due to their stability, physicochemical properties and applications. Controlling gold nanoparticles with atomic precision is of significance for subsequent research on their structures, properties and applications, which is a dream that has been pursued for many years since ruby gold was first obtained by Faraday in 1857. Fortunately, this dream has recently been partially realized for some ultrasmall gold nanoparticles (nanoclusters). However, rationally designing and synthesizing gold nanoparticles with atomic precision are still distant goals, and this challenge might rely primarily on rich atomically precise gold nanoparticle libraries and the in-depth understanding of metal nanoparticle chemistry. Herein, we review general synthesis strategies and some facile synthesis methods, with an emphasis on the controlling parameters determined from well-documented results, which might have important implications for future nanoparticle synthesis with atomic precision and facilitate related research and applications.

The synthesis strategy, methods and parameters for atomically precise gold nanoclusters were reviewed, and future outlook was also proposed.     

Electrochemical synthesis and properties of gold nanomaterials

Approximately two decades ago, gold catalyst opened up a new view of their properties when they are introduced in the form of nanomaterials, since at that time, many approaches to preparation and use of gold nanoparticles started to be used in many practical applications. Today, the research activity relating to gold nanomaterials is becoming systematic and goes further to make connections between their surface structure, chemical and physical properties, and possible applications. Since electrodeposition is one of the most controllable methods used to prepare nanoparticles, nanowires, and nanoclusters of gold, the present review gives preference on their electrochemical synthesis. The relationship between catalytic activity, size, morphology and stability of gold nanomaterials is discussed in detail. Based on the properties of the prepared gold nanocatalysts, their new applications in chemical, photochemical, and electrochemical reactions have been observed.     

Design of oxide nanoparticles by aqueous chemistry

The elaboration of nanoparticles designed for technological applications in various fields such as catalysis, optics, magnetism, electronics… needs the strict control of their characteristics, especially chemical composition, crystalline structure, size, and shape. These characteristics bring the physical properties (color, magnetism, band gap…) of the material, and also the surface to volume ratio of particles which is of high importance when they are used as a chemically active or reactive support, in catalysis for instance. The nanoparticles may have also to be surface functionalized by various species, and/or dispersed in aqueous or non aqueous media. We will show that the aqueous chemistry of metal cations is a very versatile and attractive way for the design of oxide nanomaterials, allowing the control of size, shape, and crystalline structure for polymorphic materials. Aqueous surface chemistry, including adsorption of various species, may be used to modify the morphology of nanoparticles. In some cases, redox processes can be involved to control the morphology of nanoparticles. Technologically important nanomaterials such as titania, alumina, and iron oxides are studied.     

Dendron-protected Au nanoparticles--effect of dendritic structure on chemical stability

A series of gold nanoparticles stabilised by 'Newkome-type' dendritic branching has been synthesised and fully characterised. In particular, the properties and behaviour of these hybrid materials are compared with those of a previously reported set of nanoparticles stabilised by dendrons constructed using l-lysine building blocks. The rates of cyanide-induced nanoparticle decomposition were determined, and it was found that the rate of decomposition increased on the introduction of dendritic branching. Furthermore, 'Newkome-type' dendrons were significantly more effective at protecting the encapsulated gold nanoparticle than the l-lysine based dendrons. It is proposed that this observation can be explained on the basis of more effective packing and surface coverage by the 'Newkome-type' dendrons. Importantly, this study therefore demonstrates that the organic chemical structure of dendritic ligands plays a crucial role in controlling the reactivity of self-assembled hybrid nanostructures.     

The golden age: gold nanoparticles for biomedicine

Gold nanoparticles have been used in biomedical applications since their first colloidal syntheses more than three centuries ago. However, over the past two decades, their beautiful colors and unique electronic properties have also attracted tremendous attention due to their historical applications in art and ancient medicine and current applications in enhanced optoelectronics and photovoltaics. In spite of their modest alchemical beginnings, gold nanoparticles exhibit physical properties that are truly different from both small molecules and bulk materials, as well as from other nanoscale particles. Their unique combination of properties is just beginning to be fully realized in range of medical diagnostic and therapeutic applications. This critical review will provide insights into the design, synthesis, functionalization, and applications of these artificial molecules in biomedicine and discuss their tailored interactions with biological systems to achieve improved patient health. Further, we provide a survey of the rapidly expanding body of literature on this topic and argue that gold nanotechnology-enabled biomedicine is not simply an act of 'gilding the (nanomedicinal) lily', but that a new 'Golden Age' of biomedical nanotechnology is truly upon us. Moving forward, the most challenging nanoscience ahead of us will be to find new chemical and physical methods of functionalizing gold nanoparticles with compounds that can promote efficient binding, clearance, and biocompatibility and to assess their safety to other biological systems and their long-term term effects on human health and reproduction (472 references).     

Gold nanoparticles as efficient antimicrobial agents for Escherichia coli and Salmonella typhi

Background

It is imperative to eliminate bacteria present in water in order to avoid problems in healthy. Escherichia coli and Salmonella typhi bacteria are two common pollutants and they are developing resistance to some of the most used bactericide. Therefore new biocide materials are being tested. Thus, gold nanoparticles are proposed to inhibit the growth of these two microorganisms.

Results

Gold nanoparticles were supported onto clinoptilolite, mordenite and faujasite zeolites. Content of gold in materials varied between 2.3 and 2.8 wt%. The size, dispersion and roughness of gold nanoparticles were highly dependent of the zeolite support. The faujasite support was the support where the 5 nm nanoparticles were highly dispersed. The efficiency of gold-zeolites as bactericides of Escherichia coli and Salmonella typhi was determined by the zeolite support.

Conclusions

Gold nanoparticles dispersed on zeolites eliminate Escherichia coli and Salmonella typhi at short times. The biocidal properties of gold nanoparticles are influenced by the type of support which, indeed, drives key parameters as the size and roughness of nanoparticles. The more actives materials were pointed out Au-faujasite. These materials contained particles sized 5 nm at surface and eliminate 90–95% of Escherichia coli and Salmonella typhi colonies.     

Advances in the Interfacial Assembly of Mesoporous Silica on Magnetite Particles

Interfacing magnetic particles with ordered mesoporous materials is an effective direction for the development of functional porous composite materials with rationally designed core–shell structures. Owing to the combined properties of magnetic nanoparticles and mesoporous silica (high surface area, large pore volume, porosity, and biocompatibility), core–shell magnetic mesoporous silica materials have generated tremendous interest in various disciplines, including chemistry, materials, bioengineering, and biomedicine. Interfacial assembly strategies enable the rational construction of magnetic mesoporous silica materials with well‐defined core–shell structure, morphology, pore parameters, and surface wettability, which can decisively influence their physical and chemical properties and thus improve their application performance. This Minireview summarizes recent progress in the synthesis of core–shell magnetic mesoporous silica and the adjustment of key parameters, including pore size, morphology, and pore orientation.     

Green synthesis of biogenic metal nanoparticles by terrestrial and aquatic phototrophic and heterotrophic eukaryotes and biocompatible agents

The size, shape and controlled dispersity of nanoparticles play a vital role in determining the physical, chemical, optical and electronic properties attributing its applications in environmental, biotechnological and biomedical fields. Various physical and chemical processes have been exploited in the synthesis of several inorganic metal nanoparticles by wet and dry approaches viz., ultraviolet irradiation, aerosol technologies, lithography, laser ablation, ultrasonic fields, and photochemical reduction techniques. However, these methodologies remain expensive and involve the use of hazardous chemicals. Therefore, there is a growing concern for the development of alternative environment friendly and sustainable methods. Increasing awareness towards green chemistry and biological processes has led to a necessity to develop simple, cost-effective and eco-friendly procedures. Phototrophic eukaryotes such as plants, algae, and diatoms and heterotrophic human cell lines and some biocompatible agents have been reported to synthesize greener nanoparticles like cobalt, copper, silver, gold, bimetallic alloys, silica, palladium, platinum, iridium, magnetite and quantum dots. Owing to the diversity and sustainability, the use of phototrophic and heterotrophic eukaryotes and biocompatible agents for the synthesis of nanomaterials is yet to be fully explored. This review describes the recent advancements in the green synthesis and applications of metal nanoparticles by plants, aquatic autotrophs, human cell lines, biocompatible agents and biomolecules.     

Nanoparticles,Proteins, and Nucleic Acids: Biotechnology Meets Materials Science

Based on fundamental chemistry, biotechnology and materials science have developed over the past three decades into today's powerful disciplines which allow the engineering of advanced technical devices and the industrial production of active substances for pharmaceutical and biomedical applications. This review is focused on current approaches emerging at the intersection of materials research, nanosciences, and molecular biotechnology. This novel and highly interdisciplinary field of chemistry is closely associated with both the physical and chemical properties of organic and inorganic nanoparticles, as well as to the various aspects of molecular cloning, recombinant DNA and protein technology, and immunology. Evolutionary optimized biomolecules such as nucleic acids, proteins, and supramolecular complexes of these components, are utilized in the production of nanostructured and mesoscopic architectures from organic and inorganic materials. The highly developed instruments and techniques of today's materials research are used for basic and applied studies of fundamental biological processes.     

Gold Nanoparticles for Biology and Medicine

Gold colloids have fascinated scientists for over a century and are now heavily utilized in chemistry, biology, engineering, and medicine. Today these materials can be synthesized reproducibly, modified with seemingly limitless chemical functional groups, and, in certain cases, characterized with atomic‐level precision. This Review highlights recent advances in the synthesis, bioconjugation, and cellular uses of gold nanoconjugates. There are now many examples of highly sensitive and selective assays based upon gold nanoconjugates. In recent years, focus has turned to therapeutic possibilities for such materials. Structures which behave as gene‐regulating agents, drug carriers, imaging agents, and photoresponsive therapeutics have been developed and studied in the context of cells and many debilitating diseases. These structures are not simply chosen as alternatives to molecule‐based systems, but rather for their new physical and chemical properties, which confer substantive advantages in cellular and medical applications.     

Gold nanoparticles for the development of clinical diagnosis methods

The impact of advances in nanotechnology is particularly relevant in biodiagnostics, where nanoparticle-based assays have been developed for specific detection of bioanalytes of clinical interest. Gold nanoparticles show easily tuned physical properties, including unique optical properties, robustness, and high surface areas, making them ideal candidates for developing biomarker platforms. Modulation of these physicochemical properties can be easily achieved by adequate synthetic strategies and give gold nanoparticles advantages over conventional detection methods currently used in clinical diagnostics. The surface of gold nanoparticles can be tailored by ligand functionalization to selectively bind biomarkers. Thiol-linking of DNA and chemical functionalization of gold nanoparticles for specific protein/antibody binding are the most common approaches. Simple and inexpensive methods based on these bio-nanoprobes were initially applied for detection of specific DNA sequences and are presently being expanded to clinical diagnosis. Figure Colorimetric DNA/RNA detection using salt induced aggregation of AuNP-DNA nanoprobes.     

Monodispersed core-shell Fe3O4@Au nanoparticles

The ability to synthesize and assemble monodispersed core-shell nanoparticles is important for exploring the unique properties of nanoscale core, shell, or their combinations in technological applications. This paper describes findings of an investigation of the synthesis and assembly of core (Fe(3)O(4))-shell (Au) nanoparticles with high monodispersity. Fe(3)O(4) nanoparticles of selected sizes were used as seeding materials for the reduction of gold precursors to produce gold-coated Fe(3)O(4) nanoparticles (Fe(3)O(4)@Au). Experimental data from both physical and chemical determinations of the changes in particle size, surface plasmon resonance optical band, core-shell composition, surface reactivity, and magnetic properties have confirmed the formation of the core-shell nanostructure. The interfacial reactivity of a combination of ligand-exchanging and interparticle cross-linking was exploited for molecularly mediated thin film assembly of the core-shell nanoparticles. The SQUID data reveal a decrease in magnetization and blocking temperature and an increase in coercivity for Fe(3)O(4)@Au, reflecting the decreased coupling of the magnetic moments as a result of the increased interparticle spacing by both gold and capping shells. Implications of the findings to the design of interfacial reactivities via core-shell nanocomposites for magnetic, catalytic, and biological applications are also briefly discussed.     

A Universal Approach for the Reversible Phase Transfer of Hydrophilic Nanoparticles

The ability to engineer the surface properties of magnetic nanoparticles is important for their various applications, as numerous physical and chemical properties of nanoscale materials are seriously affected by the chemical constitution of their surfaces. For some specific applications, nanoparticles need to be transferred from a polar to a nonpolar environment (or vice versa) after synthesis. In this work we have developed a universal method for the phase transfer of magnetic nanoparticles that preserves their shape and size. Octadecyltrimethoxysilane was used to cap the surfaces of the aqueous magnetic nanoparticles, thereby allowing their transfer into nonpolar solution. The resulting hydrophobic magnetic nanoparticles were transferred back into aqueous solution by subsequently covering them with an egg‐PC lipid monolayer. The superparamagnetic properties of the particles were retained after the phase transfer. The maximum transfer yields are dependent on their particle size with a maximum value of 93.16±4.75 % for magnetic nanoparticles with a diameter of 100 nm. The lipid‐modified magnetic particles were stable over 1 week, and thus they have potential applications in the field of biomedicine. This work also provides a facile strategy for the controllable engineering of the surface properties of nanoparticles.     

Photochemical Synthesis of Gold and Silver Nanoparticles—A Review

Nanomaterials have supported important technological advances due to their unique properties and their applicability in various fields, such as biomedicine, catalysis, environment, energy, and electronics. This has triggered a tremendous increase in their demand. In turn, materials scientists have sought facile methods to produce nanomaterials of desired features, i.e., morphology, composition, colloidal stability, and surface chemistry, as these determine the targeted application. The advent of photoprocesses has enabled the easy, fast, scalable, and cost- and energy-effective production of metallic nanoparticles of controlled properties without the use of harmful reagents or sophisticated equipment. Herein, we overview the synthesis of gold and silver nanoparticles via photochemical routes. We extensively discuss the effect of varying the experimental parameters, such as the pH, exposure time, and source of irradiation, the use or not of reductants and surfactants, reagents’ nature and concentration, on the outcomes of these noble nanoparticles, namely, their size, shape, and colloidal stability. The hypothetical mechanisms that govern these green processes are discussed whenever available. Finally, we mention their applications and insights for future developments.