Ammonia Synthesis with Visible Light and Quantum Dots.

Light-assisted synthesis of ammonia from nitrate and nitrite sources is a sustainable approach to reduce the burden of the energy-intensive Haber-Bosch process. However, poor selectivity and the need for UV-active photocatalysts are the current bottlenecks in the synthesis of ammonia from nitrate and nitrite sources. Herein, we introduce selective visible-light-driven ammonia production from nitrate and nitrite ions with indium phosphide quantum dots (InP QDs) as the photocatalyst.

Plasmon-powered chemistry with visible-light active copper nanoparticles.

In the quest for affordable materials for performing visible-light driven chemistry, we report here intriguing optical and photothermal properties of plasmonic copper nanoparticles (CuNPs). Precise tuning of reaction conditions and surface functionalization yield stable and monodisperse CuNPs, with a strong localized surface plasmon absorption at ∼580 nm. The molar extinction coefficient is estimated to be ∼7.

Plasmonic Nanoparticles Boost Solar-to-Electricity Generation at Ambient Conditions.

Sunlight-to-electricity conversion using solar thermoelectric generators (STEGs) is a proven technology to meet our ever-growing energy demand. However, STEGs are often operated under a vacuum with customized thermoelectric materials to achieve high performance. In this work, the incorporation of plasmonic gold nanoparticle (AuNP) based solar absorbers enabled the efficient operation of STEGs under ambient conditions with commercially available thermoelectric devices.

Metal-semiconductor heterojunction accelerates the plasmonically powered photoregeneration of biological cofactors.

Photocatalysis with plasmonic nanoparticles (NPs) is emerging as an attractive strategy to make and break chemical bonds. However, the fast relaxation dynamics of the photoexcited charge carriers in plasmonic NPs often result in poor yields. The separation and extraction of photoexcited hot-charge carriers should be faster than the thermalization process to overcome the limitation of poor yield.

Plasmon enabled Claisen rearrangement with sunlight.

Plasmonic-heat generated from the solar irradiation of gold nanoparticles is used as the thermal energy source for the Claisen rearrangement of allyl phenyl ether to 2-allylphenol, which is conventionally performed with electrical heating at 250 °C. The use of a closed reactor enables the physical separation of the reactants from the source of plasmonic-heat, thereby preventing the interference of the hot-charge carriers in the plasmon-driven Claisen rearrangement. In this way, the sole effect of plasmonic-heat in driving a high temperature organic transformation is demonstrated.

What Triggers the Dynamic Self-Assembly of Molecules and Materials?

Dynamic self-assembly has emerged as one of the reliable approaches to create complex materials with more life-like functions. In a typical dynamic self-assembly process, the external triggers activate the building blocks to initiate the assembly step to form transiently stable higher-order structures. These external triggers provide a constant supply of energy to maintain the transiently stable self-assembled states.

Blue-emitting InP quantum dots participate in an efficient resonance energy transfer process in water.

Development of stable blue-emitting materials has always been a challenging task because of the necessity of high crystal quality and good optical properties. We have developed a highly efficient blue-emitter, based on environmentally friendly indium phosphide/zinc sulphide quantum dots (InP/ZnS QDs) in water, by controlling the growth kinetics of the core as well as the shell. A rational combination of less-reactive metal-halides, phosphorus, and sulphur precursors is the key for achieving the uniform growth of the InP core and ZnS shell.

Nanoparticle Self-Assembly: From Design Principles to Complex Matter to Functional Materials.

The creation of matter with varying degrees of complexities and desired functions is one of the ultimate targets of self-assembly. The ability to regulate the complex interactions between the individual components is essential in achieving this target. In this direction, the initial success of controlling the pathways and final thermodynamic states of a self-assembly process is promising.

Electrostatically Directed Long-Range Self-Assembly of Nucleotides with Cationic Nanoparticles To Form Multifunctional Bioplasmonic Networks.

Precise control over interparticle interactions is essential to retain the functions of individual components in a self-assembled superstructure. Here, we report the design of a multifunctional bioplasmonic network via an electrostatically directed self-assembly process involving adenosine 5'-triphosphate (ATP). The present study unveils the ability of ATP to undergo a long-range self-assembly in the presence of cations and gold nanoparticles (AuNP).

Temporal Changes in Interparticle Interactions Drive the Formation of Transiently Stable Nanoparticle Precipitates.

We demonstrate the power of fine-tuned interparticle interactions, emanating from appropriately functionalized surfaces, in creating self-assembled structures that show a transient switching between completely precipitated and redispersed stages of nanoparticles (NPs). The pH-dependent temporal changes in the strength of electrostatic interactions are explored to unveil a transient self-assembly response in plasmonic NPs. The assembly process was triggered by the electrostatic attraction between positively charged gold NPs (AuNPs) and an aggregating agent, ethylenediaminetetraacetic acid (EDTA).

Electrostatically Driven Resonance Energy Transfer in an All-Quantum Dot Based Donor-Acceptor System.

Demonstration of fundamental photophysical properties in environmentally friendly quantum dots (QDs) is essential to realize their practical use in various light harvesting applications. We accomplish here an efficient light induced resonance energy transfer in all-QD based donor-acceptor system in water, deprived of any commonly used organic dye component. Our nanohybrid system comprises surface engineered indium phosphide/zinc sulfide (InP/ZnS) QD as the donor, and copper indium sulfide/zinc sulfide (CIS/ZnS) QD as the acceptor.

Multicolor Luminescent Patterning via Photoregulation of Electron and Energy Transfer Processes in Quantum Dots.

Ability to create high-contrast multicolor luminescent patterns is essential to realize the full potential of quantum dots (QDs) in display technologies. The idea of using a nonemissive state is adopted in the present work to enhance the color-contrast of QD-based photopatterns. This is achieved at a multicolor level by the photoregulation of electron and energy transfer processes in a single QD nanohybrid film, composed of one QD donor and two dye acceptors.

Photoluminescence Quenching in Self-Assembled CsPbBr Quantum Dots on Few-Layer Black Phosphorus Sheets.

An ordered self-assembly of CsPbBr quantum dots (QDs) was generated on the surface of few-layer black phosphorus (FLBP). Strong quenching of the QD fluorescence was observed, and analyzed by time-resolved photoluminescence (TR-PL) studies, DFT calculations, and photoconductivity measurements. Charge transfer by type I band alignment is suggested to be the cause of the observed effects.

Electrostatically driven resonance energy transfer in "cationic" biocompatible indium phosphide quantum dots.

Indium Phosphide Quantum Dots (InP QDs) have emerged as an alternative to toxic metal ion based QDs in nanobiotechnology. The ability to generate cationic surface charge, without compromising stability and biocompatibility, is essential in realizing the full potential of InP QDs in biological applications. We have addressed this challenge by developing a place exchange protocol for the preparation of cationic InP/ZnS QDs.

Engineering Gram Selectivity of Mixed-Charge Gold Nanoparticles by Tuning the Balance of Surface Charges.

Nanoparticles covered with ligand shells comprising both positively and negatively charged ligands exhibit Gram-selective antibacterial action controlled by a single experimental parameter, namely the proportion of [+] and [-] ligands tethered onto these particles. Gram selectivity is attributed to the interplay between polyvalent electrostatic and non-covalent interactions that work in unison to disrupt the bacterial cell wall. The [+/-] nanoparticles are effective in low doses, are non-toxic to mammalian cells, and are tolerated well in mice.

Self-assembly of like-charged nanoparticles into microscopic crystals.

Like-charged nanoparticles, NPs, can assemble in water into large, faceted crystals, each made of several million particles. These NPs are functionalized with mixed monolayers comprising ligands terminating in carboxylic acid group ligands as well as positively charged quaternary ammonium ligands. The latter groups give rise to electrostatic interparticle repulsions which partly offset the hydrogen bonding between the carboxylic acids.

Synthesis of toroidal gold nanoparticles assisted by soft templates.

A three-component system comprising surfactant molecules and molecularly cross-linked metal centers assembles into nanoring structures. The thickness of the nanorings is determined by the dimensions of the surfactant bilayer while the dimensions of the ring opening depend on and can be regulated by the concentrations of the participating species. Once formed, these organic-inorganic hybrids can be transformed, by air plasma treatment, into all-metal nanorings exhibiting strong adsorption in the near IR.

Colloidal assembly directed by virtual magnetic moulds.

Interest in assemblies of colloidal particles has long been motivated by their applications in photonics, electronics, sensors and microlenses. Existing assembly schemes can position colloids of one type relatively flexibly into a range of desired structures, but it remains challenging to produce multicomponent lattices, clusters with precisely controlled symmetries and three-dimensional assemblies. A few schemes can efficiently produce complex colloidal structures, but they require system-specific procedures.

Controlled pH stability and adjustable cellular uptake of mixed-charge nanoparticles.

Nanoparticles functionalized with mixed self-assembled monolayers (m-SAMs) comprising positively and negatively charged thiols are stable at both low and high pH but precipitate sharply at the pH where the charges on the particle are balanced (pH(prec)). By adjusting the proportion of the positively and negatively charged ligands in the m-SAM or changing particle size, pH(prec) can be varied flexibly between ~4 and ~7. In addition, changes in the SAMs' composition and particles' net charge translate into different degrees of cellular uptake.

Nanostructural anisotropy underlies anisotropic electrical bistability.

Regular arrays of nanorods having asymmetric cross-sections are fabricated by a combination of electrodeposition and glancing-angle deposition (GLAD). When these nanorods are embedded in a polymer matrix, they give rise to composite materials in which the structural anisotropy at the nanoscale translates into functional anisotropy in the form of direction-dependent electrical bistability. The degree of this directional bistability depends on and can be controlled by the spacing between the nearby nanorods.