Janus Nanoparticle Emulsions as Chiral Nanoreactors for Enantiomerically Selective Ligand Exchange

Janus nanoparticles capped with a hydrophobic and hydrophilic hemisphere of mercapto ligands can self‐assemble into hollow, emulsion‐like nanostructures in controlled media. As the nanoparticle emulsions are chiroptically active exhibiting a plasmonic circular dichroism absorption in the visible range, they can be exploited as a unique chiral nanoreactor by selective encapsulation of d ‐enantiomer into the water phase of the water‐in‐oil emulsions for directional functionalization of the nanoparticles and endow the resulting nanoparticles with select chirality. This is demonstrated in the present study with gold Janus nanoparticles functionalized with (hydrophobic) hexanethiolates and (hydrophilic) 3‐mercapto‐1,2‐propandiol, and d ,l ‐cysteine is used as the molecular probe. Experimental results demonstrate that d ‐cysteine is the preferred enantiomers entrapped within the nanoparticle emulsions, where the ensuing ligand exchange reaction is initially confined to the hydrophilic face of the Janus nanoparticles. This suggests that with a deliberate control of the reaction time, chiral Janus nanoparticles can be readily prepared by ligand exchange reactions even with a racemic mixture of ligands.     

Formation of palladium nanoparticles in poly (o-methoxyaniline) macromolecule fibers: An in-situ chemical synthesis method

We report here a novel in-situ synthetic method for the preparation of poly (o-methoxyaniline) and palladium nanoparticle composite material. Ortho-Methoxyaniline and palladium acetate were used as the precursors; during the reaction o-methoxyaniline was oxidized and forms poly (o-methoxyaniline) and palladium acetate is reduced forming palladium nanoparticles. IR and Raman spectra provide information on the structure of the polymer. The TEM and SEM analysis are used to determine the size of the nanoparticles and the morphology of the polymer respectively.     

Negative refractive index in chiral spiral metamaterials at terahertz frequencies

A three-dimensional chiral metamaterial consisting of arrays of the multi-layered mutually twisted metallic spirals is proposed. We theoretically demonstrate such a chiral spiral structure exhibiting negative refractive index at terahertz frequencies. The chirality with varied refractive index can be obtained by change of configurations of the structure. The presented design offers flexibility for investigation of electromagnetic properties of chiral metamaterials in the terahertz regime and thus leads to a unique route to terahertz device applications.     

Fabrication of optically tunable silica nanocapsules containing Ag/Au nanostructures by confined galvanic replacement reaction

Abstract  

Silica nanocapsules containing Ag/Au alloy nanostructures (SNCAs) are fabricated by galvanic replacement (GR) reactions between silver core nanoparticles within silica shells and aqueous HAuCl₄ in a confined nano-space. The structure and morphology of the resulting SNCAs are diversified by controlling the relative amount of Ag/Au, exhibiting tunable optical absorptions in visible region. The GR reactions in a confined nano-space include alloying and de-alloying processes that determine the evolution of morphology and optical absorption of SNCAs.     

Non-equilibrium cation distribution and enhanced spin disorder in hollow CoFe2O4 nanoparticles

We present magnetic properties of hollow and solid CoFe(2)O(4) nanoparticles that were obtained by annealing of Co(33)Fe(67)/CoFe(2)O(4) (core/shell) nanoparticles. Hollow nanoparticles were polycrystalline whereas the solid nanoparticles were mostly single crystal. Electronic structure studies were performed by photoemission which revealed that particles with hollow morphology have a higher degree of inversion compared to solid nanoparticles and the bulk counterpart. Electronic structure and the magnetic measurements show that particles have uncompensated spins. Quantitative comparison of saturation magnetization (M(S )), assuming bulk Néel type spin structure with cationic distribution, calculated from quantitative XPS analysis, is presented. The thickness of uncompensated spins is calculated to be significantly large for particles with hollow morphology compared to solid nanoparticles. Both morphologies show a lack of saturation up to 7 T. Moreover magnetic irreversibility exists up to 7 T of cooling fields for the entire temperature range (10-300 K). These effects are due to the large bulk anisotropy constant of CoFe(2)O(4) which is the highest among the cubic spinel ferrites. The effect of the uncompensated spins for hollow nanoparticles was investigated by cooling the sample in large fields of up to 9 T. The magnitude of horizontal shift resulting from the unidirectional anisotropy was more than three times larger than that of solid nanoparticles. As an indication signature of uncompensated spin structure, 11% vertical shift for hollow nanoparticles is observed, whereas solid nanoparticles do not show a similar shift. Deconvolution of the hysteresis response recorded at 300 K reveals the presence of a significant paramagnetic component for particles with hollow morphology which further confirms enhanced spin disorder.     

Computer simulations of the condensation of nanoparticles from the gas phase

The crystallization of Ni nanoclusters from the gas phase is investigated with the help of molecular dynamics simulations using empirical tight-binding potentials. In these simulations, the condensation of hot liquid droplets from the gas phase is observed which later crystallize and agglomerate. It is shown that agglomeration of crystallized particles is the dominating growth mode and that the shapes of the final particles are similar to the shapes of experimentally grown Ni nanoparticles. In the second part, the evolution of the structure and the morphology of an agglomerated particle during sintering at 600 and 900K is studied. While in both cases the original disordered interface between the agglomerated particles vanishes, the shapes of the resulting particles differ considerably due to the different surface diffusion rates.     

Green synthesis of palladium nanoparticles using broth of Cinnamomum camphora leaf

The development of dependable, environmentally benign processes for the synthesis of nanoscale materials is an important aspect of nanotechnology. In the present study, we report one-pot biogenic fabrication of palladium nanoparticles by a simple procedure using broth of Cinnamomum camphora leaf without extra surfactant, capping agent, and/or template. The mean size of palladium nanoparticles, ranging from 3.2 to 6.0 nm, could be facilely controlled by merely varying the initial concentration of the palladium ions. The polyols components and the heterocyclic components were believed to be responsible for the reduction of palladium ions and the stabilization of palladium nanoparticles, respectively.     

One-step synthesis of porous palladium nanostructures by H2+He arc plasma method

Porous palladium nanostructures were prepared on a copper sheet previously fixed over the plasma high-temperature area by H₂+He arc plasma method. However, dispersed palladium nanoparticles with diameters in 50–90 nm were obtained on the inner wall of vacuum chamber. SEM, TEM, EDXA, XRD and BET were employed to characterize the palladium porous materials. SEM images show that porous palladium nanostructures are composed of spherical particles with diameters of 35 ± 3 nm. This special structure with large surface to volume ratio can be recycled easily for application in the field of catalysis.     

Metal-enhanced fluorescence of graphene oxide by palladium nanoparticles in the blue-green part of the spectrum

Graphene oxide(GO) has a wide fluorescence bandwidth,which makes it a prospective candidate for numerous applications.For many of these applications,the fluorescence yield of GO should be further increased.The sp~2-hybridized carbons in GO confine the π-electrons.Radiative recombination of electron-hole pairs in such sp~2 clusters is the source of fluorescence in this material.Palladium nanoparticles are good catalysts for sp~2 bond formations.We report on the preparation of GO,palladium nanoparticles and their nanocomposites in two different solvents.It is shown that palladium nanoparticles can considerably enhance the intrinsic fluorescence of GO in the blue-green part of the visible light spectrum.Fluorescence enhancement has been attributed to the catalytic role of palladium nanoparticles in increasing the number of sp2 bonds of GO with the molecules of the surrounding media.It is shown that palladium nanoparticles could be the nanoparticle of choice for fluorescence enhancement of GO because of their catalytic role in sp2 bond formation.     

Tunable Polycyclic Chiral Beams

The generation of polycyclic chiral beams by inducing annular spiral zone phases that consist of multiple subphases is numerically and experimentally demonstrated. Each subphase is composed of a spiral phase, an equiphase, and a radial phase. The number and twisting direction of the spiral intensity lobes for every layer could be individually controlled. Furthermore, the orientations for the twisting lobes could be tuned by changing the introduced equiphase gradient. More importantly, such optical fields also show rotation property when the equiphases with gradient are dynamically and continuously imposed. This advantage of rotation also brings about the possibility of such chiral beams to rotate particles. Such beams would be advantageous for manufacturing tunable chiral metamaterials and have potential applications in optical tweezers and optical communication.     

Palladium nanoparticles on silica-rich substrates by spontaneous reduction at room temperature

Metallic palladium nanoparticles (<5 nm) have been spontaneously obtained from an acid solution of palladium chloride salt on silica-rich substrates (sepiolite, microfibrous silica, fumed silica, and milled silica glass) without any additional reduction treatment. Variable proportions of metallic palladium were straightforwardly obtained, depending on the nature of the substrate. The presence of a large amount of silanol groups acting as nucleation centers, seem to be a requisite to obtain small Pd nanoparticles. Additionally, an absorbance maximum associated to a surface plasmon resonance corresponding to the spherical particles of metallic palladium has been identified at a wavelength of 238 nm. The large specific surface of the employed substrates with the palladium nanoparticles suggest that these materials could be used for gas catalysis.     

Hydrogen-induced Ostwald ripening at room temperature in a Pd nanocluster film

The structural and morphological changes occurring in an ensemble of vapor deposited palladium nanoclusters have been studied after several hydrogenation cycles with x-ray diffraction, extended x-ray-absorption fine structure spectroscopy, Rutherford backscattering spectrometry, and STM. Initial hydrogenation increased the cluster size, a result that is attributed to hydrogen-induced Ostwald ripening. This phenomenon originates from the higher mobility of palladium atoms resulting from the low sublimation energy of the palladium hydride as compared to that of the palladium metal. The universality of this phenomenon makes it important for the application of future nanostructured hydrogen storage materials.     

The role of the solvent in the ultrashort laser ablation of palladium target in liquid

In the present study, the pulsed laser ablation in liquid technique was used to produce palladium nanoparticles in acetone and in water. The composition, morphology and oxidation state of the obtained nanoparticles have been characterized by HR-TEM, XPS and XRD techniques. The results evidence that the nature of the solvent influences the physical–chemical properties of the products. In acetone non-aggregate metallic nanoparticles have been obtained, while in water the oxidation of the particles surface is present, as showed by the XPS analysis. Moreover, the particles obtained in water are aggregated and the coalescence effect is evident. The different size distributions of nanoparticles obtained in the two liquids have been interpreted considering the different cavitation bubble dynamics.     

Hetergeneous-nucleation synthesis of monodisperse ε-cobalt nanoparticles using palladium seeds

Monodisperse bimetallic Pd–Co nanoparticles were prepared via a thermal decomposition of cobalt carbonyl using palladium seeds at the Pd/Co molar ratios 0.5%, 1%, and 5%. The heterogeneously nucleated nanoparticles without any size-selective precipitation are sufficiently uniform to self-assemble into ordered arrays. The as-synthesized nanoparticles are each a single crystal with a complex cubic structure called ε-Co. The presence of Pd seeds seems to improve the stability of Co nanoparticles against oxidation based on the results from time-dependent magnetization measurement.     

The morphology of mass selected ruthenium nanoparticles from a magnetron-sputter gas-aggregation source

We have investigated the morphology of mass selected ruthenium nanoparticles produced with a magnetron-sputter gas-aggregation source. The nanoparticles are mass selected using a quadrupole mass filter, resulting in narrow size distributions and average diameters between 2 and 15 nm. The particles are imaged in situ by scanning electron microscopy and scanning tunneling microscopy (STM) as well as ex-situ using transmission electron microscopy (TEM). For each distribution of mass selected nanoparticles, the height determined by STM and the width determined by TEM are seen to be similar throughout the mass range investigated. The particles are found to have a well-defined morphology for diameters below approximately 6 nm. Larger nanoparticles are less well-defined having rough surfaces, unlike the equilibrium morphology determined from the Wulff construction. The morphology of the particles is, in general, believed to be determined by the conditions inside the gas-aggregation source and the morphology is retained as the particles are soft-landed on the substrate.     

Spiral spin order of self-assembled Co nanodisk arrays

Spin order in hexagonal close packed cobalt nanodisk rows is quantitatively determined by off-axis electron holography. Periodic variation in the density of the local magnetic flux shows features of a spiral spin arrangement along the row axis, resulting from a tilted magnetic moment of nanoparticles with respect to the nanodisk axis.     

Random lasing from dye-doped chiral nematic liquid crystals in oriented and non-oriented cells

These are the experimental results describing random lasing in dye-doped chiral nematic liquid crystals. A novel random lasing emission is studied in this article based on the helical domains of dye-doped chiral nematic liquid crystals in oriented and non-oriented cells. Under frequency doubled 532 nm Nd:YAG (yttrium aluminum garnet) laser-pumped optical excitation, we carefully observed and analysed random lasing from dye-doped chiral nematic liquid crystals with wavelength ranges from 600 nm to 620 nm. In addition, the line-width of multi-mode peaks is less than 0.2 nm. The difference between the two random lasing behaviours in the oriented and non-oriented cells arises from the fact that random lasing appearing in the oriented cell results from stronger multiple scattering of light generated by the spiral domains of the liquid crystal molecules. Furthermore, chiral nematic liquid crystal micro-domains with different orientations can induce variation of the diffusion constant, thereby resulting in a decrease or increase in the lasing intensity of the random lasers, and an increase or decrease in their energy thresholds. In addition, a detailed comparison of the two experimental results is also presented in the article, showing the dependence of the lasing threshold and the number of lasing modes on the transport mean free path, the excited area, and the sample size. This process allows us to obtain a random laser by changing the structure of the sample, realising tunable random lasers at low cost.     

Nonequilibrium self-organization phenomena in active Langmuir monolayers

Langmuir monomolecular layers, formed by amphiphilic molecules at liquid-air interfaces and containing a fraction of chiral molecules, are theoretically investigated. These monolayers can be brought out of thermal equilibrium by applying a gradient of small molecules across the interface, resulting in the leakage flow. We show that, when splay coupling between the orientation field and the local concentration of chiral molecules in the monolayer is taken into account, this nonequilibrium soft matter system can show complex wave behavior, including the development of target wave patterns, spiral waves, and dense regions filled with inwardly propagating waves.     

Nanostructure of laser-deposited palladium thin films on different substrates

The morphological features of palladium thin films deposited on different substrates are described. Film deposition has been performed by means of the pulsed laser evaporation method. It is shown that the grain structure of palladium films is formed independently of the substrate roughness. Particular emphasis is placed on the correlation between gas-sensitive metal-insulator-semiconductor (MIS) sensor properties and the nanostructure of palladium films used as metal electrodes in these sensors. It is concluded that a change in the morphology of palladium films has no direct influence on the degradation of the hydrogen sulphide sensitivity of MIS sensors that arises after sensor annealing in air enriched with hydrogen.     

Enantiospecific adsorption of chiral molecules on chiral gold clusters

Enantioselectivity in gold clusters is investigated by studying the adsorption of a chiral amino acid (cysteine) on a chiral Au55 cluster using density functional calculations. The highest adsorption energies were found when the amino and thiolate functional groups of cysteine are bonded to the lowest coordinated edges of the chiral cluster. Enantiospecific adsorption is primarily obtained from the different bond location and strength, at the cluster edge, of the carboxyl groups forming the left- and right-handed enantiomers. These results provide theoretical support to convey enantioselectivity in asymmetric nanocatalysts using chiral gold clusters.