Reinout Meijboom

Synthesis and characterization of Cu, Ag and Au dendrimer-encapsulated nanoparticles and their application in the reduction of 4-nitrophenol to 4-aminophenol

Here, we report on the synthesis, characterization and catalytic evaluation of Cu, Ag and Au dendrimer encapsulated nanoparticles (DENs). Generations 4-6 of PAMAM-OH and PAMAM-NH(2) were used as templating agents for the synthesis of Cu and Ag-DENs respectively. Generation 4 PAMAM-NH(2) dendrimers were used for the synthesis of Au-DENs. These prepared DENs were characterized using UV visible (UV-vis) spectroscopy as well as a high resolution transmission electron microscopy (HRTEM). The catalytic activity of these DENs was evaluated on the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AMP) by sodium borohydride (NaBH(4)). The reaction was monitored by UV-vis spectroscopy at λ 400 nm. These prepared DENs were found to exhibit good activity for this reduction reaction.

Preparation of Well-Defined Dendrimer Encapsulated Ruthenium Nanoparticles and Their Evaluation in the Reduction of 4‑Nitrophenol According to the Langmuir−Hinshelwood Approach

This study discusses the preparation of various sized dendrimer encapsulated ruthenium nanoparticles (RuDEN) with the use of the generation 4 (G4), generation 5 (G5), and generation 6 (G6) hydroxyl-terminated poly(amidoamine) (PAMAM-OH) dendrimers as templating agents. The size of the nanoparticles ranges from 1.1 to 2.2 nm. These catalysts were fully characterized using UV/vis spectrophotometry, infrared (IR) spectroscopy, and transmission electron microscopy (TEM). The RuDEN catalysts were evaluated in the reduction of 4-nitrophenol (4NP) in the presence of sodium borohydride (BH4(-)) for various concentrations of either. The kinetic data obtained were modeled to the Langmuir-Hinshelwood equation. The model allows the relation of the apparent rate constant to the total surface area S of the nanoparticle, the kinetic constant k which is related to the rate-determining step, and the adsorption constants K(4NP) and K(BH4) for 4NP and borohydride, respectively. These parameters were calculated for each of the RuDENs, proving the Langmuir-Hinshelwood model to be suitable for the kinetic evaluation of RuDENs in the catalytic reduction of 4NP.

Dendrimer-templated Pd nanoparticles and Pd nanoparticles synthesized by reverse microemulsions as efficient nanocatalysts for the Heck reaction: A comparative study.

Palladium nanoparticles (NPs) were prepared using a dendrimer-templated method using G4, G5 and G6 PAMAM-OH dendrimers as well as a reverse microemulsion method using the water/dioctyl sulfosuccinate sodium salt (aerosol-OT, AOT) surfactant/isooctane system with water to surfactant ratios (ω0) of 5, 10 and 13. These 6 catalysts were characterized by UV-Vis spectroscopy, TEM, EDX, and XRD. TEM micrographs showed that the average sizes of 2.74-3.32nm with narrower size distribution were achieved by using dendrimer-templated synthetic methods, whereas the reverse microemulsion method resulted in broad size distribution with an average size of 3.87-5.06nm. The influence of various reaction parameters such as base, catalyst dosing, alkene, aryl halide and temperature on the Heck C-C coupling reaction was evaluated. The activation parameters were derived from the reaction rate of each catalyst obtained at various temperatures. A correlation of catalytic activity, enthalpy of activation and particle size is discussed. Particle size changes of each catalyst were investigated after the catalytic reaction. Overall results indicated that dendrimer-templated Pd NP catalysts showed superior activity as compared to the Pd NPs synthesized by reverse microemulsions, with the dendrimer-templated G5-OH(Pd80) showing the best activity. These catalysts were also reusable for 3 cycles, retaining high yield and showing excellent yields under mild conditions. Therefore, the dendrimer-templated Pd NPs are efficient catalyst systems for the ligand-free Heck C-C coupling reaction.

Synergistic Effects of Gold–Palladium Nanoalloys and Reducible Supports on the Catalytic Reduction of 4-Nitrophenol

Herein we report on the catalytic activity of mesoporous nickel, iron, cerium, cobalt, and manganese oxides prepared using KIT-6 as a hard template via evaporation-assisted precipitation. The mesoporous metal oxides (MMOs) were characterized and used as heterogeneous catalysts in the reduction of 4-nitrophenol (4-Nip) by sodium borohydride (BH4-). Furthermore, polyamidoamide (PAMAM) dendrimers were used to synthesize gold-palladium nanoalloy particles. The size of AuPd/PAMAM was found to be 3.5 ± 0.8 nm in diameter before being immobilized on the aforementioned mesoporous metal oxides and used as catalysts in the reduction of 4-Nip. Prior to catalytic evaluation, the reduction profiles of the mesoporous metal oxides were investigated by hydrogen-temperature-programmed reduction (H2-TPR) and showed that mesoporous metal oxides can be easily reduced at lower temperatures and that the immobilization of gold-palladium nanoalloy particles lowers their reduction temperatures. Mesoporous cobalt and manganese oxides showed catalytic activity toward 4-Nip reduction, and the activity was enhanced after immobilization of the gold-palladium nanoalloys. Isolation of nanoparticles activity was achieved by immobilization of the gold-palladium nanoalloys on the inert silica support. From this we postulated an electron relay mechanism for the reduction of 4-nitrophenol. With the use of power rate law we showed that 4-Nip reduction follows pseudo-first-order kinetics.

Catalytic Behavior of Different Sizes of Dendrimer-Encapsulated Aun Nanoparticles in the Oxidative Degradation of Morin with H2O2

Different sizes of icosahedral-like dendrimer-encapsulated Au nanoparticles (Au55- and Au147-DENs) were prepared in the presence of generation 6 amine-terminated dendrimers (G6-PAMAM-NH2) as a template. The synthesis is carried out by the complexation of a Au metal precursor (AuHCI4) with the tertiary amine groups within the dendrimer framework. The addition of excess reducing agent, NaBH4, results in the formation of Au nanoparticles encapsulated within the dendrimer cavities. The as-prepared catalysts were characterized using UV-visible (UV-vis) spectroscopy, high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray analysis (EDX), and Fourier transform infrared (FTIR). The average sizes of Au55- and Au147-DENs were determined to be 1.7 ± 0.4 and 2.0 ± 0.3 nm, respectively. The catalytic activity of these Au-DEN catalysts was evaluated in the oxidative decomposition of morin by H2O2. Since morin has a maximum absorption band at λ 410 nm at pH 10, this catalyzed oxidation process was monitored by time-resolved UV-vis spectroscopy. The catalytic activities of these two catalysts were compared by fitting the kinetic data to the Langmuir-Hinshelwood model. This model allows the determination of adsorption constants of both morin (K(morin)) and H2O2 (K(H2O2)) on the catalyst surface. A full kinetic study for this Au-DEN-catalyzed oxidative degradation of morin is reported.

Thermal stability of Ti–MCM-41

Ti containing mesoporous MCM-41 materials have been synthesized through two methods: heating and non-heating [room temperature (RT)]. The synthesized materials have been characterized using X-ray diffraction, Fourier transform infrared, nitrogen sorption, and X-ray fluorescence methods and their thermal stabilities evaluated using thermogravimetric methods in inert atmosphere. The thermal stabilities have been analyzed based on the synthesis method, as well as on the amount of titanium in the MCM-41 materials. The thermal stability results suggest that uncalcined MCM-41 materials generally show higher mass loss than their calcined counterparts. Also, the RT-synthesized materials showed lower stability than the high-temperature synthesized samples for the uncalcined samples. It is also been found that MCM-41 materials show improved thermal stabilities as the amount of titanium is increased.

Concomitant polymorphic behavior of di-μ-thiocyanato-κ2N:S;κ2S:N-bis[bis(tri-p-fluorophenylphosphine-κP)silver(I)]

The structures of two polymorphs, both monoclinic P2(1)/n [polymorph (I)] and P2(1)/c [polymorph (II)], of di-mu-thiocyanato-kappa(2)N:S;kappa(2)S:N-bis[bis(tri-p-fluorophenylphosphine-kappaP)silver(I)] complexes have been determined at 100 K. In both polymorphs the complex has a dinuclear structure where the silver(I) coordinates to two phosphine ligands and two bridging thiocyanate anions to form complexes with distorted tetrahedral geometry. Polymorph (I) has just one half of the [Ag(2)(SCN)(2){P(4-FC(6)H(4))(3)}(4)] molecule at (0, 1/2, 0) from the origin in the asymmetric unit. Polymorph (II) has one and a half molecules of [Ag(2)(SCN)(2){P(4-FC(6)H(4))(3)}(4)] in the asymmetric unit; the half molecule is situated at (0, 1, 1/2), while the full molecule is located at (1/3, 1/2, 1/3) from the origin. The Ag-P bond distances range from 2.4437 (4) to 2.4956 (7) A in both polymorphs. The Ag-S distances are 2.5773 (7) A in (I) and 2.5457 (5), 2.5576 (5) and 2.5576 (5) A in (II). The full molecule in polymorph (II) has slightly shorter Ag-N bond distances [2.375 (1) and 2.367 (2) A] compared with the half molecules in both polymorphs [2.409 (2) A in (II) and 2.395 (2) A in (I)]. The two polymorphs are compared using r.m.s. overlay calculations as well as half-normal probability plot analysis.

Effects of Daniella oliveri Wood Flour Characteristics on the Processing and Functional Properties of Wood Polymer Composites

The effects of particle sizes/distribution and contents on the processing, changes in microstructure and functional properties of wood polymer composites (WPCs) prepared from virgin high-density polyethylene (vHDPE) and sodium hydroxide (NaOH) treated Daniella oliveri wood flour via compression molding have been explored. Findings from this study suggested that an appropriate choice of wood flour characteristics could improve the interactions between the wood flour and the vHDPE matrix by eliminating incomplete wetting, segregation, and agglomeration of wood flour particles during processing while enhancing mechanical and thermal properties of the composites. Properties of the WPCs were optimized when wood flour of particle sizes/distribution and contents of +210–300 µm and 35 wt%, respectively, were blended with vHDPE matrix.

Isomorphism in monomeric 1:3 complexes of silver(I) salts with tri-p-tolylphosphine.

Reaction of silver(I) salts with three equivalents of tri-p-tolylphosphine in CH(3)CN resulted in a series of isomorphous complexes [AgX{P(4-MeC(6)H(4))(3)}(3)] (X = Br, SCN, ClO(4)). These complexes all crystallize in the orthorhombic space group Pna2(1). The complexes with X = Br, SCN are distorted tetrahedral around the silver(I) atom, whereas the ClO(4)(-) complex is distorted trigonal planar around the silver. The new complexes are compared with each other using r.m.s. overlay calculations as well as half-normal probability plot analysis and with the previously reported isomorphous chloride, bromide as well as the non-isomorphous iodide complexes.

The effect of 1:2 Ag(I) thiocyanate complexes in MCF-7 breast cancer cells

There is much interest currently in the design of metal compounds as drugs and various metal compounds are already in clinical use. These include gold(I) compounds such as auranofin and the anti-cancer platinum(II) complex, cisplatin. Bis-chelated gold(I) phosphine complexes have also shown great potential as anticancer agents, however, their efficacy has been limited by their high toxicity. In this study, silver(I) thiocyanate compounds linked to four specific ligands, were synthesized and characterized. These silver-phosphine adducts included [AgSCN{P(4-MeC6H4)3}2]2 (1); [AgSCN{P(4-ClC6H4)3}2]2 (2); [AgSCN{P(4-MeOC6H4)3}2]2 (3); [AgSCN(PPh3)2]2 (4). The compounds were found to be toxic to MCF-7 breast cancer cells while the ligands on their own were not toxic. Our findings further indicate that the silver(I) phosphine compounds induce apoptotic cell death in these breast cancer cells. In addition, the compounds were not toxic to nonmalignant fibroblast cells at the IC50 concentrations. This is an indication that the compounds show selectivity towards the cancer cells.