Magnetically Induced CO2 Methanation Using Exchange-Coupled Spinel Ferrites in Cuboctahedron-Shaped Nanocrystals.

Magnetically induced catalysis can be promoted taking advantage of optimal heating properties from the magnetic nanoparticles to be employed. However, when unprotected, these heating agents that are usually air-sensitive, get sintered under the harsh catalytic conditions. In this context, we present, to the best of our knowledge, the first example of air-stable magnetic nanoparticles that: 1) show excellent performance as heating agents in the CO2 methanation catalyzed by Ni/SiRAlOx, with CH4 yields above 95 %, and 2) do not sinter under reaction conditions. To attain both characteristics we demonstrate, first the exchange-coupled magnetic approach as an alternative and effective way to tune the magnetic response and heating efficiency, and second, the chemical stability of cuboctahedron-shaped core-shell hard CoFe2 O4 -soft Fe3 O4 nanoparticles.

Unveiling nanometer scale extinction and scattering phenomena through combined electron energy loss spectroscopy and cathodoluminescence measurements.

Plasmon modes of the exact same individual gold nanoprisms are investigated through combined nanometer-resolved electron energy-loss spectroscopy (EELS) and cathodoluminescence (CL) measurements. We show that CL only probes the radiative modes, in contrast to EELS, which additionally reveals dark modes. The combination of both techniques on the same particles thus provides complementary information and also demonstrates that although the radiative modes give rise to very similar spatial distributions when probed by EELS or CL, their resonant energies appear to be different. We trace this phenomenon back to plasmon dissipation, which affects in different ways the plasmon signatures probed by these techniques. Our experiments are in agreement with electromagnetic numerical simulations and can be further interpreted within the framework of a quasistatic analytical model. We therefore demonstrate that CL and EELS are closely related to optical scattering and extinction, respectively, with the addition of nanometer spatial resolution.

Room-temperature ferromagnetism in antiferromagnetic cobalt oxide nanooctahedra.

Cobalt oxide octahedra were synthesized by thermal decomposition. Each octahedron-shaped nanoparticle consists of an antiferromagnetic CoO core enclosed by eight {111} facets interfaced to a thin (∼ 4 nm) surface layer of strained Co3O4. The nearly perfectly octahedral shaped particles with 20, 40, and 85 nm edge length show a weak room-temperature ferromagnetism that can be attributed to ferromagnetic correlations appearing due to strained lattice configurations at the CoO/Co3O4 interface.

Multiwalled carbon nanotubes drive the activity of metal@oxide core-shell catalysts in modular nanocomposites.

Rational nanostructure manipulation has been used to prepare nanocomposites in which multiwalled carbon nanotubes (MWCNTs) were embedded inside mesoporous layers of oxides (TiO(2), ZrO(2), or CeO(2)), which in turn contained dispersed metal nanoparticles (Pd or Pt). We show that the MWCNTs induce the crystallization of the oxide layer at room temperature and that the mesoporous oxide shell allows the particles to be accessible for catalytic reactions. In contrast to samples prepared in the absence of MWCNTs, both the activity and the stability of core-shell catalysts is largely enhanced, resulting in nanocomposites with remarkable performance for the water-gas-shift reaction, photocatalytic reforming of methanol, and Suzuki coupling. The modular approach shown here demonstrates that high-performance catalytic materials can be obtained through the precise organization of nanoscale building blocks.

Surface plasmon mapping of dumbbell-shaped gold nanorods: the effect of silver coating.

We report on the identification of surface plasmons in individual gold dumbbell-shaped nanoparticles (AuDBs), as well as AuDBs coated with silver. We use spatially resolved electron energy-loss spectroscopy in a scanning electron microscope, which allows us to map plasmon-energy and intensity spatial distributions. Two dominant plasmon resonances are experimentally resolved in both AuDBs and silver-coated AuDBs. The intensity of these features is peaked either at the tips or at the sides of the nanoparticles. We present boundary element method simulations in good agreement with the experiment, allowing us to elucidate the nature of such modes. While the lower-energy, tip-focused plasmon is of longitudinal character for all dumbbells under consideration, the second side-bound plasmon has a more involved symmetry, starting as a longitudinal quadrupole in homogeneous AuDBs and picking up transversal components when silver coating is added. The longitudinal dipolar mode energy is found to blue-shift upon coating with silver. We find that the substrate produces sizable shifts in the plasmons of silver-coated AuDBs. Our analysis portraits a complex plasmonic scenario in metal nanoparticles coated with silver, including a transition from the original homogeneous gold dumbbell plasmons to the modes of homogeneous silver rods. We believe that these findings can have potential application to plasmon engineering.

Highly active nanoreactors: nanomaterial encapsulation based on confined catalysis.

It happens inside: highly active nanoreactors are prepared by encapsulating dendritic Pt nanoparticles (NPs) grown on a polystyrene template inside hollow porous silica capsules. The catalytic activity of these Pt NPs is preserved after encapsulation and template removal. Different metals, such as Ni, can thus be reduced inside the capsules, thereby leading to the formation of composites with tunable magnetic properties.

Novel small stable gold nanoparticles bearing fluorescent cysteine-coumarin probes as new metal-modulated chemosensors.

Emissive molecular probes based on amino acid moieties are very appealing because of their application as new building blocks in peptide synthesis. Two new bioinspired coumarin probes (L1 and L2) were synthesized and fully characterized by elemental analysis, infrared, (1)H NMR, (13)C NMR, UV-vis absorption and emission spectroscopy, matrix-assisted laser desorption-ionization time-of-flight mass spectrometry (MALDI-TOF-MS), lifetime measurements, and X-ray crystal diffraction. Their sensing ability toward alkaline earth, transition, and post-transition metal ions (Ca(2+), Zn(2+), Cd(2+), Cu(2+), Ni(2+), Hg(2+), Ag(+), and Al(3+)) and their acid-base behavior (H(+), OH(-)) were explored in absolute ethanol by absorption and fluorescence spectroscopy. Compound L1 shows a strong complexation constant with the soft metal ions Zn(2+), Cd(2+), and Ag(+). Compound L2 shows a high fluorescence quantum yield, and it could be used as a non-pH-dependent fluorescent biological probe. Very small gold nanoparticles (AuNPs) using compounds L1 and L2 as stabilizers were obtained by using a reductive method and were characterized by UV-vis, light scattering, and transmission electron microscopy (TEM). Dynamic light scattering and TEM studies show that the formation of small nanoparticles is around 4.27 ± 0.64 nm for L1 and around 2.69 ± 0.96 nm for L2. The new stable Cou@AuNPs behaved as supramolecular chemosensors, which have been selective for the heavy element Hg(2+), with a concomitant change of color from pink to dark red/brown and an increase of size up to 100-fold.

Design of SERS-encoded, submicron, hollow particles through confined growth of encapsulated metal nanoparticles.

The synthetic architectures of complex inorganic nanostructures, including multifunctional hollow capsules, are expected to play key roles in many different applications, such as drug delivery, photonic crystals, nanoreactors, and sensing. Implementation of novel strategies for the fabrication of such materials is needed because of the infancy of this knowledge, which still limits progress in certain areas. Herein we report a straightforward synthetic approach for the development of multifunctional submicron reactors comprising catalytic gold nanoparticles (2-3 nm) confined inside hollow silica capsules. Additionally, the confined growth of encapsulated metal nanoparticles was carried out to evidence the usefulness and functionality of these reactors in catalytic applications and as an approach for the development of novel complex nanostructures. Their potential and multifunctionality have been pointed out by fabrication of SERS-encoded submicrometer particles with shape and size uniformity for use in antigen biosensing; this was accomplished via codification of gold nanoparticle islands grown onto their inner surfaces.

Effects of elastic anisotropy on strain distributions in decahedral gold nanoparticles.

Metallic nanoparticles exhibit exceptional optoelectronic properties with applications in plasmonics, biosensing and nanomedicine. Recently, new synthesis techniques have enabled precise control over the sizes and shapes of metal nanoparticles, occasionally leading to morphologies that cannot be properly characterized using standard techniques. An example is five-fold-twinned decahedral Au nanoparticles, which are intrinsically strained as a result of their unique geometry. Various competing models have been proposed to predict the strain states of such nanoparticles. Here, we present a detailed analysis of the internal structure of a decahedral Au nanoparticle using aberration-corrected high-resolution electron microscopy and strain mapping. Our measurements confirm the presence of a disclination, which is consistent with the commonly accepted strain model. However, we also observed shear gradients, which are absent from the models. By comparing our local strain determinations with finite-element calculations, we show the effect of elastic anisotropy on the strain state in these nanoparticles.

Loading of exponentially grown LBL films with silver nanoparticles and their application to generalized SERS detection.

Feature film: Thin films made by exponential layer-by-layer growth display high diffusivity and can be readily infiltrated with inorganic nanoparticles. They can sequestrate molecular systems from solution as a function of the composition of their layers, while providing intense surface-enhanced Raman scattering (SERS) signals (see picture).

Evidence of direct crystal growth and presence of hollow microspheres in magnetite particles prepared by oxidation of Fe(OH)2.

We provide new information relevant to the crystallinity and growth mechanism of magnetite particles that were fabricated following the method of Sugimoto and Matijevic [J. Colloid Interface Sci. 74 (1980) 227]. These authors observed that in a small excess of Fe(2+), particles grew by aggregation and recrystallization of smaller units, so that until now the resulting particles were thought to be polycrystalline. With the help of transmission electron microscopy (TEM) and selected area electron diffraction (SAED), we also detected the presence of monocrystalline particles, which are strong evidence of the occurrence of direct crystal growth. This growth mechanism seems to coexist with that of the aggregation of primary units proposed by Sugimoto and Matijevic. Careful examination of electron microscopy micrographs also revealed the presence of many hollow polycrystalline microspheres.

Toxicological Evaluation of Luminescent Silica Nanoparticles as New Drug Nanocarriers in Different Cancer Cell Lines.

Luminescent mesoporous silica nanoparticles, CdTeQDs@MNs@PEG1, SiQDs@Isoc@MNs and SiQDs@Isoc@MNs@PEG2, were successfully synthetized and characterized by SEM, TEM, XRD, N2 nitrogen isotherms, ¹H NMR, IR, absorption, and emission spectroscopy. Cytotoxic evaluation of these nanoparticles was performed in relevant in vitro cell models, such as human hepatoma HepG2, human brain endothelial (hCMEC/D3), and human epithelial colorectal adenocarcinoma (Caco-2) cell lines. None of the tested nanoparticles showed significant cytotoxicity in any of the three performed assays (MTT/NR/ LDH) compared with the respective solvent and/or coating controls, excepting for CdTeQDs@MNs@PEG1 nanoparticles, where significant toxicity was noticed in hCMEC/D3 cells. The results presented reveal that SiQDs-based mesoporous silica nanoparticles are promising nanoplatforms for cancer treatment, with a pH-responsive drug release profile and the ability to load 80% of doxorubicin.

Engineered Nanostructured Materials for Ofloxacin Delivery.

Antibiotic resistance is emerging as a growing worldwide problem and finding solutions to this issue is becoming a new challenge for scientists. As the development of new drugs slowed down, advances in nanotechnology offer great opportunities, with the possibility of designing new systems for carrying, delivery and administration of drugs already in use. Engineered combinations of the synthetic, broad-spectrum antibiotic ofloxacin, rarely studied in this field, with different types of silver, mesoporous silica-based and Pluronic/silica-based nanoparticles have been explored. The nanocarriers as silver core@silica mesoporous (AgMSNPs) and dye-doped silica nanoparticles functionalized with ofloxacin were synthesized and their antibacterial properties studied against S. aureus and E. coli. The best antibacterial results were obtained for the AgMSNPs nanosystem@ofloxacin for the strain S. aureus ATCC 25923, with MIC and MBC values of 5 and 25 µg/mL, proving the efficacy and synergetic effect of the antibiotic and the Ag core of the nanoparticles.

Plasmonic Retrofitting of Membrane Materials: Shifting from Self-Regulation to On-Command Control of Fluid Flow.

This work calls for a paradigm shift in order to change the operational patterns of self-regulated membranes in response to chemical signals. To this end, the fabrication of a retrofitting material is introduced aimed at developing an innovative generation of porous substrates endowed with symbiotic but fully independent sensing and actuating capabilities. This is accomplished by transferring carefully engineered plasmonic architectures onto commercial microfiltration membranes lacking of such features. The integration of these materials leads to the formation of a coating surface proficient for ultrasensitive detection and "on-command" gating. Both functionalities can be synergistically modulated by the spatial and temporal distribution of an impinging light beam offering an unprecedented control over the membrane performance in terms of permeability. The implementation of these hybrid nanocomposites in conventional polymeric porous materials holds great potential in applications ranging from intelligent fluid management to advanced filtration technologies and controlled release.

Shaping iron oxide nanocrystals for magnetic separation applications.

Iron oxide nanostructures are attractive for a variety of bio-related applications given their wide range of magnetic properties. Here, we report on the study of the magnetophoretic mobility of octapod-shaped nanocrystals, which we relate to stoichiometry, quality and elongation in the 111 direction of these cubic structures. This special morphology combines magnetocrystalline anisotropies, increases shape anisotropy and hinders the formation of an epitaxial wüstite-magnetite interface. As a result, one obtains nanocrystals with large magnetic susceptibility and small coercivity, that is, with optimum characteristics for magnetic guidance, separation, and drug delivery, due to the increased magnetophoretic mobility displayed.

Redispersion and Self-Assembly of C60 Fullerene in Water and Toluene.

This work aims at assessing the influence of two different solvents, bidistilled water and toluene, on dispersions of carbon-based engineered nanomaterials, namely, fullerenes, and their self-assembly behavior. The obtained self-assembled carbon-based materials were characterized using UV-vis spectrophotometry and transmission electron microscopy techniques. The results obtained were unexpected when toluene was used for dispersing fullerene C60, with the formation of two different types of self-assembled structures: fullerene C60 nanowhiskers (FNWs) and a type of quasispherical nanostructure. The FNWs ranged between 1 and 6 µm in length, whereas the quasispherical fullerene C60 nanoaggregates ranged between 10 and 50 nm in diameter. Aggregates obtained in toluene showed a well-formed crystal structure. When using water, the obtained aggregates were amorphous and showed a no well-defined shape. Their sizes ranged between 20 and 40 nm for nanosized structures and between 0.4 and 4.8 µm for micron-sized self-aggregates.

Synthesis and Characterization of PtTe2 Multi-Crystallite Nanoparticles using Organotellurium Nanocomposites.

Herein, we report the synthesis of new PtTe2 multi-crystallite nanoparticles (NPs) in different sizes through an annealing process using new nanostructured Pt-Te organometallic NPs as a single source precursor. This precursor was obtained in a single reaction step using Ph2Te2 and H2PtCl6 and could be successfully size controlled in the nanoscale range. The resulting organometallic composite precursor could be thermally decomposed in 1,5 pentanediol to yield the new PtTe2 multi-crystallite NPs. The final size of the multi-crystallite spheres was successfully controlled by selecting the nanoprecursor size. The sizes of the PtTe2 crystallites formed using the large spheres were estimated to be in the range of 2.5-6.5 nm. The results provide information relevant to understanding specific mechanistic aspects related to the synthesis of organometallic nanomaterials and nanocrystals based on platinum and tellurium.

Bending contours in silver nanoprisms.

A detailed electron microscopy analysis is reported on the structure of silver nanoprisms synthesized by controlled photoinduced aggregation of Ag nanoparticles. Bending of the nanoprism (111) face is directly revealed in the presence of fringes in both bright and dark field TEM images, which are unequivocally assigned to bending contours. Such contours can be individually imaged through shifting of the objective aperture and selectively allowing transmission of the corresponding diffraction spot. The assignment of a bent structure is supported by images of the lateral sides of the prisms, and high-resolution images where apparent changes in the lattice constant are observed.

Unraveling the Organotellurium Chemistry Applied to the Synthesis of Gold Nanomaterials.

Long-term preservation of the properties of gold nanoparticles in both solution and the dry powder form can be difficult. We have overcome this challenge by using organotellurium derivatives as both reducing agents and stabilizers in the synthesis of gold nanoparticles. This new synthetic protocol takes advantage of the photochemical and oxidative properties of diphenyl ditelluride (Ph2Te2), which, so far, have never been exploited in the synthesis of gold nanoparticles. The Au/Te core/shell (inorganic/organic) hybrid nanomaterial can be obtained in a one-step reaction, using only Ph2Te2 and HAuCl4. By modifying the reaction conditions, different resonance conditions of the gold core are achieved due to the formation of external shells with different thicknesses. The organotellurium shell can be easily removed by resuspension of the nanoparticles in environmentally friendly solvents, such as water or ethanol, making the Au core available for subsequent applications. A mechanism for the formation of core/shell nanoparticles has also been discussed.