Moving from surfactant-stabilized aqueous rhodium (0) colloidal suspension to heterogeneous magnetite-supported rhodium nanocatalysts: Synthesis, characterization and catalytic performance in hydrogenation reactions

Wet impregnation of pre-synthesized surfactant-stabilized aqueous rhodium (0) colloidal suspension on silica was employed in order to prepare supported Rh-0 nanoparticles of well-defined composition, morphology and size. A magnetic core-shell support of silica (Fe(3)O4@SiO2) was used to increase the handling properties of the obtained nanoheterogeneous catalyst. The nanocomposite catalyst Fe3O4@SiO2-Rh-0 NPs was highly active in the solventless hydrogenation of model olefins and aromatic substrates under mild conditions with turnover frequencies up to 143,000 h(-1). The catalyst was characterized by various transmission electron microscopy techniques showing well-dispersed rhodium nanoparticles (similar to 3 nm) mainly located at the periphery of the silica coating. The heterogeneous magnetite-supported nanocatalyst was investigated in the hydrogenation of cyclohexene and compared to the previous surfactant-stabilized aqueous Rh-0 colloidal suspension and various silica-supported Rh-0 nanoparticles. Finally, the composite catalyst could be reused in several runs after magnetic separation. (C) 2011 Elsevier B. V. All rights reserved.

Lipase-Catalyzed Kinetic Resolution of (+/-)-Mandelonitrile under Conventional Condition and Microwave Irradiation

The kinetic resolution of (+/-)-mandelonitrile was carried out using lipase from Candida antarctica under conventional condition (orbital shaker) and microwave irradiation in toluene, producing the (S)-mandelonitrile acetate with high selectivity (up to >98% ee, enantiomeric excess). The unreacted (R)-mandelonitrile under microwave irradiation and conventional condition was partially converted into benzaldehyde by spontaneous chemical equilibrium. The (S)-mandelonitrile acetate under microwave irradiation was produced with 92% ee and 35% yield for 8 h of reaction. Conventional transesterification of (+/-)-mandelonitrile in an orbital shaker produced unreacted (R) -mandelonitrile (51% ee) and (S)-mandelonitrile acetate (98% ee) in accordance with Kazlauskas rule for 184 h of reaction.

Electrocatalytic Activity of Pd, Pt, and Rh for the Electro-oxidation of Ethanol in Alkaline Electrolyte: An Online DEMS Study

The electro-oxidation of ethanol was investigated on electrodeposited layers of Pd, Pt, and Rh in alkaline electrolyte. The reaction products were monitored by experiments of online differential electrochemical mass spectrometry (DEMS). Potentiodynamic curves for the ethanol electro-oxidation catalyzed by these three different metal electrocatalysts showed similar onset potentials, but the highest Faradaic current peak was observed for the Pt electrocatalyst. Online DEMS experiments evidenced similar amounts of CO2 for the three different materials, but Pd presented the higher production of ethylacetate (acetic acid). This indicated that the electrochemical oxidation of ethanol on the Pd surface occurred to a higher extent. The formation of methane, which was observed for Pt and Rh, after potential excursions to lower potentials, was absent for Pd. On the basis of the obtained results, it was stated that, on Pt and Rh, the formation of CO2 occurs mainly via oxidation of CO and CH (x,ad) species formed after dissociative adsorption of ethanol or ethoxy species that takes place only at low potentials. This indicates that the dissociative adsorption of ethanol or ethoxy species is inhibited at higher potentials on Pt and Rh. On the other hand, on the Pd electrocatalyst, the reaction may occur via nondissociative adsorption of ethanol or ethoxy species at lower potentials, followed by oxidation to acetaldehyde and, after that, by a further oxidation step to acetic acid on the electrocatalyst surface. Additionally, in a parallel route, the acetaldehyde molecules adsorbed on the Pd surface can be deprotonated, yielding a reaction intermediate in which the carbon-carbon bond is less protected, and therefore, it can be dissociated on the Pd surface, producing CO2, after potential excursions to higher potentials.

4-Organochalcogenoyl-1H-1,2,3-triazoles: synthesis and functionalization by a nickel-catalyzed Negishi cross-coupling reaction

A general method for the synthesis of triazoles containing selenium and tellurium was accomplished via a CuCAAC reaction between organic azides and a terminal triple bond, generated by in situ deprotection of the silyl group. The reaction tolerates alkyl and arylazides, with alkyl and aryl substituents directly bonded to the chalcogen atom. The products were readily functionalized by a nickel-catalyzed Negishi cross-coupling reaction, furnishing the aryl-heteroaryl products at the 4-position in good yields. (C) 2012 Elsevier Ltd. All rights reserved.

Transesterification of Palm Oil Catalyzed by Pseudomonas fluorescens Lipase in a Packed-Bed Reactor

Transesterification of palm oil with ethanol catalyzed by Pseudomonas fluorescens lipase immobilized on epoxy-polysiloxane-polyvinyl alcohol composite (epoxy-SiO2-PVA) was performed in a continuous packed-bed reactor (PBR). Two strategies were used for improving the miscibility of the substrates: the addition of the organic solvent tert-butanol and the surfactant Triton X-100. Results were compared to those obtained in a solventless reactor, which displayed a biphasic system that passed through the reactor. Using this system, the ethyl ester yield of 61.6 +/- 1.2% was obtained at steady state. Both Triton X-100 and tert-butanol systems were found to be suitable to promote the miscibility of the starting materials; however, the use of Triton X-100 reduced the yield to levels lower than 20%, because of the enzyme desorption from the support surface, as confirmed by scanning electron microscopy analysis. The best performance was found for the reactor running in the presence of tert-butanol which resulted in a stable operating system and an average yield of 87.6 +/- 2.5%. This strategy also gave high biocatalyst operational stability, revealing a half-life of 48 days and an inactivation constant of 0.6 X 10(-3) h(-1).

Revision of Singlet Quantum Yields in the Catalyzed Decomposition of Cyclic Peroxides

The chemiluminescence of cyclic peroxides activated by oxidizable fluorescent dyes is an example of chemically initiated electron exchange luminescence (CIEEL), which has been used also to explain the efficient bioluminescence of fireflies. Diphenoyl peroxide and dimethyl-1,2-dioxetanone were used as model compounds for the development of this CIEEL mechanism. However, the chemiexcitation efficiency of diphenoyl peroxide was found to be much lower than originally described. In this work, we redetermine the chemiexcitation quantum efficiency of dimethyl-1,2-dioxetanone, a more adequate model for firefly bioluminescence, and found a singlet quantum yield (Phi(s)) of 0.1%, a value at least 2 orders of magnitude lower than previously reported. Furthermore, we synthesized two other 1,2-dioxetanone derivatives and confirm the low chemiexcitation efficiency (Phi(s) < 0.1%) of the intermolecular CIEEL-activated decomposition of this class of cyclic. peroxides. These results are compared with other chemiluminescent reactions, supporting the general trend that intermolecular CIEEL systems are much less efficient in generating singlet excited states than analogous intramolecular processes (Phi(s) approximate to 50%), with the notable exception of the peroxyoxalate reaction (Phi(s) approximate to 60%).

Effect of cellulose physical characteristics, especially the water sorption value, on the efficiency of its hydrolysis catalyzed by free or immobilized cellulase

Cellulase, an enzymatic complex that synergically promotes the degradation of cellulose to glucose and cellobiose, free or adsorbed onto Si/SiO(2) wafers at 60 degrees C has been employed as catalyst in the hydrolysis of microcrystalline cellulose (Avicel), microcrystalline cellulose pre-treated with hot phosphoric acid (CP), cotton cellulose (CC) and eucalyptus cellulose (EC). The physical characteristics such as index of crystallinity (I(C)), degree of polymerization (DP) and water sorption values were determined for all samples. The largest conversion rates of cellulose into the above-mentioned products using free cellulase were observed for samples with the largest water sorption values; conversion rates showed no correlation with either IC or DP of the biopolymer. Cellulose with large water sorption value possesses large pore volumes, hence higher accessibility. The catalytic efficiency of immobilized cellulase could not be correlated with the physical characteristics of cellulose samples. The hydrolysis rates of the same cellulose samples with immobilized cellulase were lower than those by the free enzyme, due to the diffusion barrier (biopolymer chains approaching to the immobilized enzyme) and less effective contact between the enzyme active site and its substrate. Immobilized cellulase, unlike its free counterpart, can be recycled at least six times without loss of catalytic activity, leading to higher overall cellulose conversion. (C) 2011 Elsevier B.V. All rights reserved.

Oxygen reduction reaction catalyzed by epsilon-MnO2: Influence of the crystalline structure on the reaction mechanism

The oxygen reduction reaction (ORR) was studied in KOH electrolyte on carbon supported epsilon-manganese dioxide (epsilon-MnO2/C). The epsilon-MnO2/C catalyst was prepared via thermal decomposition of manganese nitrate and carbon powder (Vulcan XC-72) mixtures. X-ray powder diffraction (XRD) measurements were performed in order to determine the crystalline structure of the resulting composite, while energy dispersive X-ray analysis (EDX) was used to evaluate the chemical composition of the synthesized material. The electrochemical studies were conducted using cyclic voltammetry (CV) and quasi-steady state polarization measurements carried out with an ultra thin layer rotating ring/disk electrode (RRDE) configuration. The electrocatalytic results obtained for 20% (w/w) Pt/C (E-TEK Inc., USA) and alpha-MnO2/C for the ORR, considered as one of the most active manganese oxide based catalyst for the ORR in alkaline media, were included for comparison. The RRDE results revealed that the ORR on the MnO2 catalysts proceeds preferentially through the complete 4e(-) reduction pathway via a 2 plus 2e(-) reduction process involving hydrogen peroxide as an intermediate. A benchmark close to the performance of 20% (w/w) Pt/C (E-TEK Inc., USA) was observed for the epsilon-MnO2/C material in the kinetic control region, superior to the performance of alpha-MnO2/C, but a higher amount of HO2- was obtained when epsilon-MnO2/C was used as catalyst. The higher production of hydrogen peroxide on epsilon-MnO2/C was related to the presence of structural defects, typical of this oxide, while the better catalytic performance in the kinetic control region compared to alpha-MnO2/C was related with the higher electrochemical activity for the proton insertion kinetics, which is a structure sensitive process. (C) 2012 Elsevier Ltd. All rights reserved.

Lipase-catalyzed kinetic resolution of beta-borylated carboxylic esters

The kinetic resolution of chiral beta-borylated carboxylic esters via lipase-catalyzed hydrolysis and transesterification reactions was studied. The enantioselective hydrolysis catalyzed by CAL-B furnished the beta-borylated carboxylic acid with reasonable enantiomeric excess (62% ee), while both methyl and ethyl beta-borylated carboxylic esters were recovered with excellent ee (>99%). Meanwhile, the transesterification reaction of beta-borylated carboxylic esters and several alcohols, catalyzed by CAL-B, only indicated a high selectivity when ethanol and methyl-(beta-pinacolylboronate)-butanoate were used as substrates, which gave ethyl-(beta-pinacolylboronate)-butanoate with >99% ee. (C) 2012 Elsevier Ltd. All rights reserved.

Ethanol steam reforming over rhodium and cobalt-based catalysts: Effect of the support

The effect of support on the properties of rhodium and cobalt-based catalysts for ethanol steam reforming was studied in this work, by comparing the use of magnesia, alumina and Mg-Al oxide (obtained from hydrotalcite) as supports. It was found that metallic rhodium particles with around 2.4-2.6 nm were formed on all supports, but Mg-Al oxide led to the narrowest particles size distribution; cobalt was supposed to be located on the support, affecting its acidity. Rhodium interacts strongly with the support in the order: alumina> Mg-Al oxide > magnesia. The magnesium-containing catalysts showed low ethene selectivity and high hydrogen selectivity while the alumina-based ones showed high ethene selectivity, assigned to the Lewis sites of alumina. The Mg-Al oxide-supported rhodium and cobalt catalyst was the most promising sample to produce hydrogen by ethanol reforming, showing the highest hydrogen yield, low ethene selectivity and high specific surface area during reaction. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

One-Pot, Three-Step Reaction of 5-[(Trimethylsilyl)ethynyl]pyrrolidin-2-one with Azides Catalyzed by Cu-I: Synthesis of a Novel Class of 1,4-Disubstituted 1,2,3-Triazoles

A very fast, easy and efficient synthesis is described for a novel and biologically important class of 1,4-disubstituted-4-(5-pyrrolidin-2-one)-1,2,3-triazoles by an ultrasound-assisted one-pot, three-step click reaction sequence of 5-[(trimethylsilyl)ethynyl]pyrrolidin-2-one with organic azides mediated by catalytic Cu-I salts.

Free Rhodium (II) citrate and rhodium (II) citrate magnetic carriers as potential strategies for breast cancer therapy

Abstract Background Rhodium (II) citrate (Rh2(H2cit)4) has significant antitumor, cytotoxic, and cytostatic activity on Ehrlich ascite tumor. Although toxic to normal cells, its lower toxicity when compared to carboxylate analogues of rhodium (II) indicates Rh2(H2cit)4 as a promising agent for chemotherapy. Nevertheless, few studies have been performed to explore this potential. Superparamagnetic particles of iron oxide (SPIOs) represent an attractive platform as carriers in drug delivery systems (DDS) because they can present greater specificity to tumor cells than normal cells. Thus, the association between Rh2(H2cit)4 and SPIOs can represent a strategy to enhance the former's therapeutic action. In this work, we report the cytotoxicity of free rhodium (II) citrate (Rh2(H2cit)4) and rhodium (II) citrate-loaded maghemite nanoparticles or magnetoliposomes, used as drug delivery systems, on both normal and carcinoma breast cell cultures. Results Treatment with free Rh2(H2cit)4 induced cytotoxicity that was dependent on dose, time, and cell line. The IC50 values showed that this effect was more intense on breast normal cells (MCF-10A) than on breast carcinoma cells (MCF-7 and 4T1). However, the treatment with 50 μM Rh2(H2cit)4-loaded maghemite nanoparticles (Magh-Rh2(H2cit)4) and Rh2(H2cit)4-loaded magnetoliposomes (Lip-Magh-Rh2(H2cit)4) induced a higher cytotoxicity on MCF-7 and 4T1 than on MCF-10A (p < 0.05). These treatments enhanced cytotoxicity up to 4.6 times. These cytotoxic effects, induced by free Rh2(H2cit)4, were evidenced by morphological alterations such as nuclear fragmentation, membrane blebbing and phosphatidylserine exposure, reduction of actin filaments, mitochondrial condensation and an increase in number of vacuoles, suggesting that Rh2(H2cit)4 induces cell death by apoptosis. Conclusions The treatment with rhodium (II) citrate-loaded maghemite nanoparticles and magnetoliposomes induced more specific cytotoxicity on breast carcinoma cells than on breast normal cells, which is the opposite of the results observed with free Rh2(H2cit)4 treatment. Thus, magnetic nanoparticles represent an attractive platform as carriers in Rh2(H2cit)4 delivery systems, since they can act preferentially in tumor cells. Therefore, these nanopaticulate systems may be explored as a potential tool for chemotherapy drug development.

Lipase-catalyzed kinetic resolution of (±)-mandelonitrile under conventional condition and microwave irradiation

The kinetic resolution of (±)-mandelonitrile was carried out using lipase from Candida antarctica under conventional condition (orbital shaker) and microwave irradiation in toluene, producing the (S)-mandelonitrile acetate with high selectivity (up to > 98% ee, enantiomeric excess). The unreacted (R)-mandelonitrile under microwave irradiation and conventional condition was partially converted into benzaldehyde by spontaneous chemical equilibrium. The (S)-mandelonitrile acetate under microwave irradiation was produced with 92% ee and 35% yield for 8 h of reaction. Conventional transesterification of (±)-mandelonitrile in an orbital shaker produced unreacted (R)-mandelonitrile (51% ee) and (S)-mandelonitrile acetate (98% ee) in accordance with Kazlauskas rule for 184 h of reaction.

Dually fluorescent silica nanoparticles

The cationic dyes 9-aminoacridine (9AA) and safranine (Sf) were entrapped into silica spheres of about 0.2 mu m diameter prepared by modified Stober method. The fluorescent materials are investigated by steady-state and time-resolved emission, in addition of confocal fluorescence microscopy. Silica particles containing 9-aminoacridine (SP9AA) and safranine (SPSf or both dyes (SPSf9AA) are emissive particles. When both dyes are present in the same particle but loaded in sequential stages 9AA emission is quenched as a consequence of energy transfer from 9AA (donor) to Sf (acceptor). This result suggests that particle growing processes where the acceptor is incorporated first into the core do not prevent donor/acceptor pairs to be close due to an overlay of the concentration gradients of both dyes in a radial core-shell like distribution. (C) 2010 Elsevier B.V. All rights reserved.

Marine Fungi Aspergillus sydowii and Trichoderma sp Catalyze the Hydrolysis of Benzyl Glycidyl Ether

Whole cells of the marine fungi Aspergillus sydowii Gc12, Penicillium raistrickii Ce16, P. miczynskii Gc5, and Trichoderma sp. Gc1, isolated from marine sponges of the South Atlantic Ocean (Brazil), have been screened for the enzymatic resolution of (+/-)-2-(benzyloxymethyl)oxirane (benzyl glycidyl ether; 1). Whole cells of A. sydowii Gc12 catalyzed the enzymatic hydrolysis of (R,S)-1 to yield (R)-1 with an enantiomeric excess (ee) of 24-46% and 3-(benzyloxy)propane-1,2-diol (2) with ee values < 10%. In contrast, whole cells of Trichoderma sp. Gc1 afforded (S)-1 with ee values up to 60% and yields up to 39%, together with (R)-2 in 25% yield and an ee of 32%. This is the first published example of the hydrolysis of 1 by whole cells of marine fungi isolated from the South Atlantic Ocean. The hydrolases from the two studied fungi exhibited complementary regioselectivity in opening the epoxide ring of racemic 1, with those of A. sydowii Gc12 showing an (S) preference and those of Trichoderma sp. Gc1 presenting an (R) preference for the substrate.