Recoverable rhodium nanoparticles: Synthesis, characterization and catalytic performance in hydrogenation reactions

We here report the first magnetically recoverable Rh(0) nanoparticle-supported catalyst with extraordinary recovery and recycling properties. Magnetic separation has been suggested as a very promising technique to improve recovery of metal-based catalysts in liquid-phase batch reactions. The separation method is significantly simple, as it does not require filtration, decantation, centrifugation, or any other separation technique thereby, overcoming traditional time- and solvent-consuming procedures. Our new magnetically separable catalytic system, comprised of Rh nanoparticles immobilized on silica-coated magnetite nanoparticles, is highly active and could be reused for up to 20 times for hydrogenation of cyclohexene (180,000 mol/mol(Rh)) and benzene (11,550 mol/mol(Rh) under mild conditions. (c) 2007 Elsevier B. V. All fights reserved.

Morphology of cobalt ferrite nanoparticle-polyelectrolyte multilayered nanocomposites

Novel magnetic nanocomposite films with controlled morphology were produced via the electrostatic layer-by-layer assembly of cationic CoFe(2)O(4) nanoparticles and anionic poly(3,4-ethylenedioxy thiophene)/poly(styrene sulfonic acid) (PEDOT:PSS) complex. The electrostatic interaction between nanoparticle and the polyelectrolyte complex ensured a stepwise growth of the nanocomposite film with virtually identical amounts of materials being adsorbed at each deposition cycle as observed by UV-vis spectroscopy. AFM images acquired under the tapping mode revealed a globular morphology with dense and continuous layers of nanoparticles with voids being filled with polymeric material. (C) 2010 Elsevier B.V. All rights reserved.

Evaluation of the Binding Properties of Maghemite Nanoparticle Surface-Coated with Meso-2-3-Dimercaptosuccinic Acid to Serum Albumin

In this study the interaction between magnetic nanoparticles (MNPs) surface-coated with meso-2,3-dimercaptosuccinic acid (DMSA) with both bovine serum albumin (BSA) and human serum albumin (HSA) was investigated. The binding of the MNP-DMSA was probed by the fluorescence quenching of the BSA and HSA tryptophan residue. Magnetic resonance and light microscopy analyses were carried out in in vivo tests using female Swiss mice. The binding constants (K(b)) and the complex stoichiometries (n) indicate that MNP-DMSA/BSA and MNP-DMSA/HSA complexes have low association profiles. After five minutes following intravenous injection of MNP-DMSA into mice`s blood stream we found the lung firstly target by the MNP-DMSA, followed by the liver in a latter stage. This finding suggests that the nanoparticle`s DMSA-coating process probably hides the thiol group, through which albumin usually binds. This indicates that biocompatible MNP-DMSA is a very promising material system to be used as a drug delivery system (DDS), primarily for lung cancer treatment.

Semiconductor nanoparticle modeling via density functional theory

In this work, a 2.0 nm nanoparticle (low limit synthesized system) is compared to possible simplified models: passivated clusters, small (1.3 nm) nanoparticles and sets of plane surfaces. Our density functional theory results suggest that even when geometric aspects are properly described by the simplifications considered, electronic properties might be very different, especially when edge atoms are not properly taken into account in the nanoparticle`s modeling. In addition, we propose a protocol that might help future theoretical descriptions of nanoparticles.

High-density gas aggregation nanoparticle gun applied to the production of SmCo clusters

We describe in this article the application of a high-density gas aggregation nanoparticle gun to the production and characterization of high anisotropy SmCo nanoparticles. We give a detailed description of the simple but efficient experimental apparatus with a focus on the microscopic processes of the gas aggregation technique. Using high values of gas flux (similar to 45 sccm) we are able to operate in regimes of high collimation of material. In this regime, as we explain in terms of a phenomenological model, the power applied to the sputtering target becomes the main variable to change the size of the clusters. Also presented are the morphological, structural, and magnetic characterizations of SmCo nanoparticles produced using 10 and 50 W of sputtering power. These values resulted in mean sizes of similar to 12 and similar to 20 nm. Significant differences are seen in the structural and magnetic properties of the samples with the 50 W sample showing a largely enhanced crystalline structure and magnetic anisotropy.

Rhodium-catalyzed carbonylation of allylaminoalcohols: Catalytic synthesis of N-(2-hydroxy-alkyl)-gamma-lactams and bicyclic oxazolidines

Gamma-lactams and bicyclic oxazolidines are important structural frameworks in both synthetic organic chemistry and related pharmacological fields. These heterocycles can be prepared by the rhodium-catalyzed carbonylation of unsaturated amines. In this work, allylaminoalcohols, derived from the aminolysis of cyclohexene oxide, styrene oxide, (R)-(+)-limonene oxide, and ethyl-3-phenyl-glicidate, were employed as substrates. These allylaminoalcohols were carbonylated by employing RhClCO(PPh3)(2) as a precatalyst under varying CO/H-2 mixtures, and moderate to excellent yields were obtained, depending on the substrate used. The results indicated that an increase in the chelating ability of the substrate (-OH and -NHR moieties) decreased the conversion and selectivity of the ensuing reaction. Additionally, the selectivity could be optimized to favor either the gamma-lactams or the oxazolidines by controlling the CO/H-2 ratio. A large excess of CO provided a lactam selectivity of up to 90%, while a H-2-rich gas mixture improved the selectivity for oxazolidines, resulting from hydroformylation/cyclization. Studies of the reaction temperature indicated that an undesirable substrate deallylation reaction occurs at higher temperature (>100 degrees C). Further, kinetic studies have indicated that the oxazolidines and gamma-lactams were formed through parallel routes. Unfortunately, the mechanism for oxazolidines formation is not yet well understood. However, our results have led us to propose a catalytic cycle based on hydroformylation/acetalyzation pathways. The gamma-lactams formation follows a carbonylation route, mediated by a rhodium-carbamoylic intermediate, as previously reported. To this end, we have been able to prepare and isolate the corresponding iridium complex, which could be confirmed by X-ray crystallographic analysis. (C) 2008 Elsevier B.V. All rights reserved.

Protoporphyrin IX Nanoparticle Carrier: Preparation, Optical Properties, and Singlet Oxygen Generation

The present study is focused on developing a nanoparticle carrier for the photosensitizer protoporphyrin IX for use in photodynamic therapy. The entrapment of protoporphyrin IX (Pp IX) in silica spheres was achieved by modification of Pp IX molecules with an organosilane reagent. The immobilized drug preserved its optical properties and the capacity to generate singlet oxygen, which was detected by a direct method from its characteristic phosphorescence decay curve at near-infrared and by a chemical method using 1,3-diphenylisobenzofuran to trap singlet oxygen. The lifetime of singlet oxygen when a suspension of Pp IX-loaded particles in acetonitrile was excited at 532 nm was determined as 52 mu s, which is in good agreement with the value determined for methylene blue in acetonitrile solution under the same conditions. The Pp IX-loaded silica particles have an efficiency of singlet oxygen generation (eta Delta) higher than the quantum yield of free porphyrins. This high efficiency of singlet oxygen generation was attributed to changes on the monomer-dimer equilibrium after photosentisizer immobilization.

Nanoparticle Platform to Modulate Reaction Mechanism of Phenothiazine Photosensitizers

Herein, we report on the synthesis of photosensitizing nanoparticles in which the generation of different oxidizing species, i.e., singlet oxygen ((1)O(2)) or radicals, was modulated. Sol gel and surface chemistry were used to obtain nanoparticles with specific ratios of dimer to monomer species of phenothiazine photosensitizers (PSs). Due to competition between the reactions involving electron transfer within dimer species and energy transfer from monomer triplets to oxygen, the efficiency of (1)O(2) generation could be controlled. Nanoparticles with an excess of dimer have an (1)O(2) generation efficiency (S(Delta)) of 0.01 while those without dimer have a S, value of 0.4. Furthermore, we demonstrate that the PS properties of the nanoparticles are not subjected to interference from the external medium as is commonly the case for free PSs, i.e., PS ground and triplet states are not reduced by NADH and ascorbate, respectively, and singlet excited states are less suppressed by bromide. The modulated (1)O(2) generation and the PS protection from external interferences make this nanoparticle platform a promising tool to aid in performing mechanistic studies in biological systems. Also, it offers potential application in technological areas in which photo-induced processes take place.

Platinum nanoparticle-modified electrodes, morphologic, and electrochemical studies concerning electroactive materials deposition

The present work describes the synthesis of platinum nanoparticles followed by their electrophoretic deposition onto transparent fluorine-doped tin oxide electrodes. The nano-Pt-modified electrodes were characterized by voltammetric studies in acidic solutions showing a great electrocatalytic behavior towards H(+) reduction being very interesting for fuel cell applications. Morphological characterization was performed by atomic force microscopy on different modified electrodes showing a very rough surface which can be tuned by means of time of deposition. Also, nickel hydroxide thin films were galvanostatically grown onto these electrodes showing an interesting electrochemical behavior as sharper peaks, indicating a faster ionic exchange from the electrolyte to the film.

Electrostatic layer-by-layer and electrophoretic depositions as methods for electrochromic nanoparticle immobilization

The present paper describes the immobilization of nanoparticles onto conducting substrates by using both electrostatic layer-by-layer and electrophoretic deposition (EPD) methods. These two techniques were compared in high-performance electrochromic electrodes based on mixed nickel hydroxide nanoparticles. In addition to easy handling, EPD seems to be the most suitable method for the immobilization of nanoparticles, leading to higher electrochromic efficiencies, lower response times and higher stability upon coloration and bleaching cycling. (C) 2008 Elsevier Ltd. All rights reserved.

Ruthenium nanoparticles prepared from ruthenium dioxide precursor: Highly active catalyst for hydrogenation of arenes under mild conditions

The hydrogenation of benzene and benzene derivatives was studied using Ru(0) nanoparticles prepared by a very simple method based on the in situ reduction of the commercially available precursor ruthenium dioxide under mild conditions (75 degrees C and hydrogen pressure 4atm) in imidazolium ionic liquids. Total turnovers (TTO) of 2700 mol/mol Ru were obtained for the conversion of benzene to cyclohexane under solventless conditions and TTO of 1200 mol/mol Ru were observed under ionic liquid biphasic conditions. When corrected for exposed ruthenium atoms, TTO values of 7940 (solventless) and 3530 (biphasic) were calculated for benzene hydrogenation. These reaction rates are higher than those observed for Ru nanoparticles prepared from decomposition of an organometallic precursor in similar conditions. The presence of the partially hydrogenated product cyclohexene was also detected at low conversion rates. (C) 2008 Elsevier B.V. All rights reserved.

Supramolecular Approach to Gold Nanoparticle/Triruthenium Cluster Hybrid Materials and Interfaces

A systematic and comprehensive study of the interaction of citrate-stabilized gold nanoparticles with triruthenium cluster complexes of general formula [Ru(3)(CH(3)COO)(6)(L)](+) [L = 4-cyanopyridine (4-CNpy), 4,4`-bipyridine (4,4`-bpy) or 4,4`-bis(pyridyl)ethylene (bpe)] has been carried out. The cluster-nanoparticle interaction in solution and the construction of thin films of the hybrid materials were investigated in detail by electronic and surface plasmon resonance (SPR) spectroscopy, Raman scattering spectroscopy and scanning electron microscopy (SEM). Citrate-stabilized gold nanoparticles readily interacted with [Ru(3)O(CH(3)COO)(6)(L)(3)](+) complexes to generate functionalized nanoparticles that tend to aggregate according to rates and extents that depend on the bond strength defined by the characteristics of the cluster L ligands following the sequence bpe > 4,4`-bpy >> 4-CNpy. The formation of compact thin films of hybrid AuNP/[Ru(3)O(CH(3)COO)(6)(L)(3)](+) derivatives with L = bpe and 4,4`-bpy indicated that the stability/lability of AuNP-cluster bonds as well as their solubility are important parameters that influence the film contruction process. Fluorine-doped tin oxide electrodes modified with thin films of these nanomaterials exhibited similar electrocatalytic activity but much higher sensitivity than a conventional gold electrode in the oxidation of nitrite ion to nitrate depending on the bridging cluster complex, demonstrating the high potential for the development of amperometric sensors.

Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)(2)((4,4 `-PO(3)H(2))(2)bpy)](2+) in TiO(2) Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru-(bpy)(2)(4,4`-(PO(3)H(2))(2)bpy)](2+) surface-bound to TiO(2) (TiO(2)-Ru(II)). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, - were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO(2)(e(-))-Ru(3+) -> TiO(2)-Ru(2+). The appearance of pH-dependent decreases in the efficiency of formation of TiO(2)-Ru(3+) and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond-microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

FiltekTM Silorane and FiltekTM Supreme XT resins: tissue reaction after subcutaneous implantation in isogenic mice

The aim of this study was to evaluate the tissue compatibility of a silorane-based resin system (FiltekTM Silorane) and a methacrylate-based nanoparticle resin (FiltekTM Supreme XT) after implantation in the subcutaneous connective tissue of isogenic mice. One hundred and thirty five male isogenic BALB/c mice were randomly assigned to 12 experimental and 3 control groups, according to the implanted material and the experimental period of 7, 21 and 63 days. At the end of each period, the animals were killed and the tubes with the surrounding tissues were removed and processed for microscopic analysis. Samples were subjected to a descriptive and a semi-quantitative analyses using a 4-point scoring system (0-3) to evaluate the collagen fiber formation and inflammatory infiltrate. Data were statistically analyzed using the Kruskal Wallis test (?=0.05). The results showed that there was no significant difference between the experimental and control groups considering the three evaluation periods (p>0.05). The silorane-based and the methacrylate-based nanoparticle resins presented similar tissue response to that of the empty tube (control group) after subcutaneous implantation in isogenic mice.

Preparation of PVP hydrogel nanoparticles using lecithin vesicles

Hydrogels micro, sub-micro and nanoparticles are of great interest for drug encapsulation and delivery or as embolotherapic agents. In this work it is described the preparation of nano and sub-microparticles of pre-formed, high molecular weight and monomer free poly(N-vinyl-2-pyrrolidone) encapsulated inside the core of lecithin vesicles. The hydrogel particles are formed with a very narrow diameter distribution, of about 800 nm, and a moderate swelling ratio, of approximately 10.