Despite the possible occurrence of metal nanoparticles in the environment due to the discharge of engineered nanoparticles and the natural transformation of metal ions into metal nanoparticles, little is known about the transformation mechanism, fates, behaviors, and effects of these nanoparticles in the environment. Here, we show that dissolved organic matter (DOM) in environmental waters can mediate the reduction of ionic Ag and Au to their metallic nanoparticles under natural sunlight, suggesting that this process may be general for metals with high reduction potential. We demonstrated that the reduction was mediated by superoxide from photoirradiation of the phenol group in DOM, and the dissolved O2 significantly enhanced the formation of Ag nanoparticles. These results imply that previous knowledge about O2-induced dissolution and its effect on persistence of Ag nanoparticles should be reconsidered in a sunlit DOM-rich aqueous environment. This study can also shed light on understanding possible natu...

Sunlight-Induced Reduction of Ionic Ag and Au to Metallic Nanoparticles by Dissolved Organic Matter

DNA metallization has witnessed tremendous growth and development, from the initial simple synthesis aimed at manufacturing conductive metal nanowires to the current fabrication of various nanostructures for applications in areas as diverse as nanolithography, energy conversion and storage, catalysis, sensing, and biomedical engineering. To this, our aim here was to present a comprehensive review to summarize the research activities on DNA metallization that have appeared since the concept was first proposed in 1998. We start with a brief presentation of the basic knowledge of DNA and its unique advantages in the template-directed growth of metal nanomaterials, followed by providing a systematic summary of the various synthetic methods developed to date to deposit metals on DNA scaffolds. Then, the leverage of DNAs with different sequences, conformations, and structures for tuning the synthesis of feature-rich metal nanostructures is discussed. Afterwards, the discussion is divided around the applications of these metal nanomaterials in the fields mentioned above, wherein the key role DNA metallization plays in enabling high performance is emphasized. Finally, the current status and some future prospects and challenges in this field are summarized. As such, this review would be of great interest to promote the further development of DNA metallization by attracting researchers from various communities, including chemistry, biology, physiology, material science, and nanotechnology as well as other disciplines.

DNA metallization: principles, methods, structures, and applications

“The possibility of using colloidal silver and gold as condensors for electron storage in artificial photosynthesis has prompted the recent renewed interest in these areas.” This statement by Fendler and co-workers in 1983 is even more relevant in today's science and technology. In this tutorial review we summarize research regarding the use of light in the synthesis of metallic nanoparticles. We describe how light of different energies induces a variety of chemical events that culminate in the nucleation and growth of metal nanocrystals. Light can thus be used as a handle to direct metal nanocrystal growth and improve tunability and reproducibility.

The relevance of light in the formation of colloidal metal nanoparticles

Silver nanoparticles (AgNPs) are the most common materials in nanotechnology-based consumer products globally. Because of the wide application of AgNPs, their potential environmental impact is currently a highly topical focus of concern. Nitrification is one of the processes in the nitrogen cycle most susceptible to AgNPs but the specific effects of AgNPs on nitrification in aquatic environments are not well understood. We report the influence of AgNPs on nitrification and associated nitrous oxide (N2O) production in estuarine sediments. AgNPs inhibited nitrification rates, which decreased exponentially with increasing AgNP concentrations. The response of nitrifier N2O production to AgNPs exhibited low-dose stimulation ( 100% at low doses of AgNPs. This result was confirmed by metatranscriptome studies showing up-regulation of nitric oxide reductase (norQ) gene expression in the low-dose treatment. Isotopomer analysis revealed that hydroxylamine oxidation was the main N2O production pathway, and its contribution to N2O emission was enhanced when exposed to low-dose AgNPs. This study highlights the molecular underpinnings of the effects of AgNPs on nitrification activity and demonstrates that the release of AgNPs into the environment should be controlled because they interfere with nitrifying communities and stimulate N2O emission.

Effects of silver nanoparticles on nitrification and associated nitrous oxide production in aquatic environments

Aggregation induced emission (AIE) has emerged as a powerful method for sensing applications. Based on AIE triggered by halogen bond (XB) formation, an ultrasensitive and selective sensor for picomolar detection of Ag nanoparticles (Ag NPs) is reported. The dye (CyI) has an iodine atom in its skeleton which functions as a halogen bond acceptor, and aggregates on the Ag NP plasmonic surfaces as a halogen bond donor or forms halogen bonds with the vacant π orbitals of silver ions (Ag+). Formation of XB leads to fluorescence enhancement, which forms the basis of the Ag NPs or Ag+ sensor. The sensor response is linearly dependent on the Ag NP concentration over the range 1.0–8.2 pM with an LOD of 6.21 pM (σ = 3), while for Ag+ it was linear over the 1.0–10 μM range (LOD = 2.36 μM). The sensor shows a remarkable sensitivity for Ag NPs (pM), compared to that for Ag+ (μM). The sensor did not show any interference from different metal ions with 10-fold higher concentrations. This result indicates that the proposed sensor is inexpensive, simple, sensitive, and selective for the detection of Ag NPs in both tap and wastewater samples.

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Halogen bond triggered aggregation induced emission in an iodinated cyanine dye for ultra sensitive detection of Ag nanoparticles in tap water and agricultural wastewater

Inspiration from chemical photography: accelerated photoconversion of AgCl to functional silver nanoparticles mediated by DNA

Although progress has been made in the construction of single-electron devices (SEDs), few of the reported approaches have proved practically applicable, mainly owing to their cost-ineffectiveness and need for sophisticated instrumentation. Herein, a conceptually new method for fabricating SEDs through the metallization of divalent DNA-nanoparticle conjugates is described. Specifically, divalent DNA copolymers that are conjugated to gold nanoparticles (AuNP) were synthesized by application of the enzymatic extension of DNA conjugated on quantum-sized AuNPs. This conjugate structure allows the distance between the resulting poly(dG)-poly(dC) and the AuNP to be controlled by an ssDNA spacer. To afford poly(dG)-poly(dC) sequence-specific metal deposition, Cisplatin capable of specific chemisorption on the poly(dG)-poly(dC) is incubated with the divalent DNA copolymer–AuNP conjugates, followed by reduction of the Cisplatin to Pt metal at base resolution. As a result, AuNPs separated from the Pt “electrodes” by the ssDNA barriers in a single conjugate could be created as a double-tunnel junction for SEDs. This study is thought to be an important step toward the programmable organization of DNA for use in SEDs.

Ayako Ishikawa

Papers

Inspiration from chemical photography: accelerated photoconversion of AgCl to functional silver nanoparticles mediated by DNA

Sequence-Specific Metallization of Single Divalent DNA–Nanoparticle Conjugates: A Potential Route to Single-Electron Devices