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. AuNPs enhanced the performance of STEG by ∼9 times, yielding an overall solar-to-electricity conversion efficiency of ∼9.6% under 7.5 W cm-2 solar irradiance at ambient conditions. Plasmonic heat dissipated by AuNPs upon solar irradiation was used as the thermal energy source for STEGs. High light absorptivity, photothermal conversion efficiency (∼95%), and thermal conductivity of AuNPs enabled the efficient generation and transfer of heat to STEGs, with minimal radiative and convective heat losses. The power generated from plasmon-powered STEGs is used to run electrical devices as well as produce green hydrogen via the electrolysis of water.

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. The withdrawal or consumption of the trigger deactivates the building block in the aggregates, thereby initiating the disassembly step. A precise control over the interplay between the deterministic and nondeterministic forces is the key to achieving a dynamic self-assembly process. This demands the appropriate choice of building blocks as well as triggers, which has led to the development of a wide range of triggers in dynamic self-assembly. Through this Perspective, we intend to highlight the functional diversities, prospects, and challenges associated with different classes of "triggers" by bringing them under one platform. Such treatment will help us to identify the missing features and deduce a guideline for the development of ideal triggers. A few of the desirable features that a trigger should possess, along with probable ways to achieve them, are discussed, as well. In summary, the Perspective covers many intriguing aspects of triggers that can be helpful for researchers to achieve precise spatiotemporal control over various interparticle interactions, which is essential to obtaining the desired outcome from a dynamic self-assembly process.

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). Modelling and NMR studies gave a qualitative insight into the major interactions driving the bioplasmonic network formation. ATP-Ca2+ coordination helps in regulating the electrostatic interaction, which is crucial in transforming an uncontrolled precipitation into a kinetically controlled aggregation process. Remarkably, ATP and AuNP retained their inherent properties in the multifunctional bioplasmonic network. The generality of electrostatically directed self-assembly process was extended to different nucleotide-nanoparticle systems.

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). The autonomous changes in the pH and ionic strength of the solution, under the influence of atmospheric CO2, weaken the aggregating ability of EDTA and initiate the complete disassembly of [+] AuNP-EDTA precipitates. The use of a nondestructive mode of autonomous disassembly helped in achieving some of the desirable feats in the field of transient self-assembly such as easy removal of waste, formation of a transiently stable precipitate state, and negligible dampness in redispersion. The chemical strategy adopted in the present work, to introduce transientness, can act as a generic tool in creating the next generation of complex matter.

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. Here we show that magnetic field microgradients established in a paramagnetic fluid can serve as 'virtual moulds' to act as templates for the assembly of large numbers (∼10(8)) of both non-magnetic and magnetic colloidal particles with micrometre precision and typical yields of 80 to 90 per cent. We illustrate the versatility of this approach by producing single-component and multicomponent colloidal arrays, complex three-dimensional structures and a variety of colloidal molecules from polymeric particles, silica particles and live bacteria and by showing that all of these structures can be made permanent. In addition, although our magnetic moulds currently resemble optical traps in that they are limited to the manipulation of micrometre-sized objects, they are massively parallel and can manipulate non-magnetic and magnetic objects simultaneously in two and three dimensions.

Photoluminescence Quenching in Self-Assembled CsPbBr3 Quantum Dots on Few-Layer Black Phosphorus Sheets.

An ordered self-assembly of CsPbBr3 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.

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. These results constitute the first example of rational engineering of Gram selectivity at the (macro)molecular level.

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. This demands the integration of rationally chosen materials to construct hybrid plasmonic photocatalysts. In this work, the enhanced photocatalytic activity of gold nanoparticle-titanium dioxide metal-semiconductor heterostructure (Au-TiO2) is used for the efficient regeneration of nicotinamide (NADH) cofactors. The modification of plasmonic AuNPs with n-type TiO2 semiconductor enhanced the charge separation process, because of the Schottky barrier formed at the Au-TiO2 heterojunction. This led to a 12-fold increment in the photocatalytic activity of plasmonic AuNP in regenerating NADH cofactor. Detailed mechanistic studies revealed that Au-TiO2 hybrid photocatalyst followed a less-explored light-independent pathway, in comparison to the conventional light-dependent path followed by sole AuNP photocatalyst. NADH regeneration yield reached ~70% in the light-independent pathway, under optimized conditions. Thus, our study emphasizes the rational choice of components in hybrid nanostructures in dictating the photocatalytic activity and the underlying reaction mechanism in plasmon-powered chemical transformations.

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 ∼7.7 × 107 M-1 cm-1 at 580 nm, which signifies their suitability for various light-harnessing studies. The characteristic wine-red colour and crystallography studies confirm the presence of mainly Cu(0) atoms in CuNPs, which showed excellent long-term colloidal and compositional stability under ambient conditions (at least 50 days). The as-synthesized oleylamine-capped CuNPs are ligand-exchanged with charged thiolate ligands of both polarities to form stable dispersions in water, with complete retention of their plasmonic properties and structural integrity (for ∼2 days and ∼6 h under inert and ambient conditions, respectively). Photothermal-conversion efficiency of CuNPs is estimated to be ∼80%, raising the surrounding temperature to ∼170 °C within ∼30 s of irradiation with a 1 W 532 nm diode laser, which is 'hot' enough to perform useful solar-vapor generation and high-temperature crystal-to-crystal phase transformation. Our work projects plasmonic CuNPs as an affordable and effective alternative to conventional metal NPs to harness light-matter interactions for future plasmon-powered chemistry.

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. Remarkably, the presence of the positively charged thiols allows for the uptake of particles having net negative charge.

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. Our study reveals the prospects of plasmonic nanostructures in conducting energy intensive chemical synthesis in a sustainable fashion.

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. The InP/ZnS QDs showed long-term stable photoluminescence (PL) in the pure-blue region (∼462 nm), with an absolute PL quantum yield of ∼50% and a colour purity of ∼80% in water. Cytotoxicity studies revealed that the cells can withstand up to ∼2 micromolar concentration of pure-blue emitting InP/ZnS QDs (∼120 µg mL-1). Multicolour imaging studies show that the PL of InP/ZnS QDs was well-retained inside the cells as well, without interfering with the fluorescence signal of commercially available biomarkers. Moreover, the ability of InP based pure-blue emitters to participate in an efficient Förster resonance energy transfer (FRET) process is demonstrated. Installing a favorable electrostatic interaction turned out to be crucial in achieving an efficient FRET process (E ∼75%) from blue-emitting InP/ZnS QDs to rhodamine B dye (Rh B) in water. The quenching dynamics fits well with the Perrin formalism and the distance-dependent quenching (DDQ) model, which confirms an electrostatically driven multi-layer assembly of Rh B acceptor molecules around the InP/ZnS QD donor. Furthermore, the process of FRET was successfully translated into the solid state, proving their suitability for device-level studies as well. In short, our study expands the spectrum of aqueous QDs based on InP towards the blue region for future biological and light harvesting studies.

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. Despite the progress made in the field, there has been a growing interest in pushing the limits of self-assembly processes. The main inception of this interest is that the intended self-assembled state, with varying complexities, may not be "at equilibrium (or at global minimum)", rendering free energy minimization unsuitable to form the desired product. Thus, we believe that a thorough understanding of the design principles as well as the ability to predict the outcome of a self-assembly process is essential to form a collection of the next generation of complex matter. The present review highlights the potent role of finely tuned interparticle interactions in nanomaterials to achieve the preferred self-assembled structures with the desired properties. We believe that bringing the design and prediction to nanoparticle self-assembly processes will have a similar effect as retrosynthesis had on the logic of chemical synthesis. Along with the guiding principles, the review gives a summary of the different types of products created from nanoparticle assemblies and the functional properties emerging from them. Finally, we highlight the reasonable expectations from the field and the challenges lying ahead in the creation of complex and evolvable matter.

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. The dominance of photoinduced electron transfer over the energy transfer process generates a nonluminescent QD nanohybrid film, which provides the black background for multicolor patterning. The superior photostability of QDs over dyes is used for the photoregulation of electron and energy transfer processes. Selective photodegradation of electron acceptor dye triggered the onset of the energy transfer process, thereby imparting a luminescent color to the QD nanohybrid film. Further, a controlled photoregulation of energy transfer process paved the way for multicolor patterning.

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. The electrostatic attraction between oppositely charged QDs is vital in achieving a strong ground state complexation in the [-] InP/ZnS:::[+] CIS/ZnS QD nanohybrid. A nonlinear Stern-Volmer plot confirms the involvement of both static and dynamic components in the PL quenching of InP/ZnS QD by CIS/ZnS QD. Moreover, a temporal evolution of resonance energy transfer is realized in the solid state as well, which can improve the potential of such "all-green QD" based nanohybrid systems for device level studies.

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. The quaternary ammonium group provides the much required permanent positive charge and stability to InP/ZnS QDs in biofluids. The two important properties of QDs, namely bioimaging and light induced resonance energy transfer, are successfully demonstrated in cationic InP/ZnS QDs. The low cytotoxicity and stable photoluminescence of cationic InP/ZnS QDs inside cells make them ideal candidates as optical probes for cellular imaging. An efficient resonance energy transfer (E ∼ 60%) is observed, under physiological conditions, between the cationic InP/ZnS QD donor and anionic dye acceptor. A large bimolecular quenching constant along with a linear Stern-Volmer plot confirms the formation of a strong ground state complex between the cationic InP/ZnS QDs and the anionic dye. Control experiments prove the role of electrostatic attraction in driving the light induced interactions, which can rightfully form the basis for future nano-bio studies between cationic InP/ZnS QDs and anionic biomolecules.

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. It is the balance between these two interactions that ultimately enables self-assembly. Depending on the pH, the particles can crystallize, form aggregates, remain unaggregated or even - in mixtures of two particle types - can "choose" whether to crystallize with like-charged or oppositely charged particles.

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.