A novel water-soluble NHC-Pd polymer: an efficient and recyclable catalyst for the Suzuki coupling of aryl chlorides in water at room temperature

A novel water-soluble NHC-Pd polymer with triethylene glycol legs was developed as a water soluble and highly recyclable catalyst that shows high catalytic activity in the Suzuki-Miyaura coupling of aryl chlorides in high yields in water at room temperature.     

A study on applications of N-substituted main-chain NHC-palladium polymers as recyclable self-supported catalysts for the Suzuki-Miyaura coupling of aryl chlorides in water

The preparation and characterization of a number of main-chain organometallic polymers (NHC-Pd MCOP) with different N-alkyl substituted groups such as benzyl (3a), n-hexyl (3b), and n-dodecyl (3c) are described. Among these polymers, 3c bearing the more lipophilic group n-dodecyl was found to be a more reactive and recoverable catalytic system in the Suzuki-Miyaura cross-coupling reaction of chloroarenes, including both deactivated and hindered aryl chlorides with different types of arylboronic acids under aqueous conditions. While the catalysts seem to be highly recyclable, on the contrary, we have provided much compelling evidence, such as kinetic monitoring, poisoning experiments, and average molecular weight determination before and after catalysis, that shows that the described organometallic polymers might be indeed the source of production of active soluble Pd species in the form of either Pd nanoparticles or fragmented NHC-Pd complexes. Our studies showed that in order to assess whether the catalysts are functioning in a heterogeneous pathway or they are simply a source of production of active Pd species, it is crucial to devise a suitable and highly efficient poison that could capture essentially soluble catalytic species. In this regard, we interestingly found that among a variety of well-known catalyst poisons such as Hg(0), SBA-15-PrSH, and cross-linked poly(4-vinylpyridine) (PVP), only PVP could efficiently quench catalysis, thus providing clear evidence of the formation soluble Pd species in our protocol. In addition, several experiments such as bright-field microscopy, dynamic light scattering (DLS) of the reaction mixture, and kinetic monitoring of the reaction at an early stage confirm not only that the described organometallic polymers could be a source of production of trace amounts of Pd nanoparticles but the capsular structures of these lipophilic polymers in water provides a means of entrapment of nanoclusters in a hydrophobic region, thus accelerating the reaction in pure water in the absence of any co-organic solvent.     

In situ formation of silver nanoparticles in PMMA via reduction of silver ions by butylated hydroxytoluene

Silver nanoparticles (Ag NPs) were efficiently generated by in situ reduction of silver ions via butylated hydroxytoluene (BHT), in poly(methyl methacrylate). The characterization of Ag/PMMA by TEM, SEM, XRD, and FTIR indicated that Ag NPs with a face center cubic (fcc) crystal structure and a mean diameter of about 30 nm were dispersed in PMMA matrix with a relatively uniform distribution. In addition, the results of UV–Vis spectroscopy indicated that optical properties of the nanocomposite appeared mainly dependent on the reaction time and temperature. Increasing the reaction time and temperature make higher yield of Ag NPs. A provisional reduction mechanism was also proposed for the formation of the Ag NPs.     

Sunlight absorbing potential of carbon nanoball water and ethylene glycol-based nanofluids

Solar thermal collectors are applicable in the water heating or space conditioning systems in which surface-based absorption of incident solar flux cause high heat losses. Therefore, an enhancement in the efficiency of solar harvesting devices is a basic challenge which requires great effort. Adding nanoparticles to the working fluid in direct absorption solar collector, which has been recently proposed, leads to improvement in the working fluid thermal and optical properties such as thermal conductivity and absorption coefficient. This results certainly in collector efficiency enhancement. In this paper, the characteristics of nanofluids consisting carbon nanoball in water- and ethylene glycol-based suspensions in consideration of their use as sunlight absorber fluid in a DASC are investigated. It was found that by using of 300 ppm carbon nanoballs, the extinction coefficient of pure water and ethylene glycol is increased by about 3.9 cm^?1 and 3.4 cm^?1 in average, respectively. With these significantly promising optical properties, a direct absorption solar collector using carbon nanoball-based nanofluids can achieve relatively higher efficiencies, compared with a conventional solar collector.     

Locally finite root supersystems

We introduce the notion of locally finite root supersystems as a generalization of both locally finite root systems and generalized root systems. We classify irreducible locally finite root supersystems.     

The effect of gamma irradiation and surfactants on the size distribution of nanoparticles based on soluble starch

The effect of three kinds of surfactants (anionic, cationic and nonionic) on the shape and size distribution of nanoparticles based on soluble starch fabricated under gamma irradiation was studied. Aqueous solution of soluble starch was irradiated with a dose of 20 kGy. The TEM micrograph and size distribution plots showed that when irradiations were made in presence of surfactants the smaller and more distinct nanoparticles were created in comparison to pure starch solution.     

Zirconium oxide (NP) - ionic liquid as an efficient media for the domino Knoevenagel hetero Diels-Alder reaction with unactivated alkynes

Immobilized ZrO₂-nanopowder (NP) in ionic liquid and different organic solvents was used as a suitable Lewis-acid for the synthesis of polycyclic heterocycles which contains pyran-based skeletons. Reaction of O-propargylated salicylaldehyde with active methylene compounds in the presence of ZrO₂-NP in ionic liquid proceeds via domino Knoevenagel hetero Diels-Alder reaction of unactivated alkynes to construct the pyran skeleton. Comparison with different ionic liquids and organic solvents showed that the best results were obtained with 1-butyl-3-methylimidazolium nitrate [bmim][NO₃] because of short reaction times and high yields. Carrying out the reaction under these conditions has advantages such as: high yields, short reaction times and easy work-up.     

Study of titanium adsorption on perfect and defected BC3 nanotubes using density functional theory

Density functional theory calculations were used to study the titanium (Ti) adsorption on perfect and defected (4, 0) BC₃ nanotubes, considering Stone–Wales and vacancy defects. The binding energy values for these nanotubes were larger than the corresponding values for carbon nanotubes. The charge transfer from the Ti atom to nanotube was observed for all systems studied. The most exothermic binding process occurred for the Ti adsorption on a native V_B defect, which showed minimum structural deformation with respect to a perfect BC₃ tube. In the case of a nanotube with a reconstructed carbon vacancy, the adsorption of Ti generated a half-metallic anti-ferromagnet. The results obtained in this paper are relevant for spintronics and hydrogen adsorption applications.     

Molecular dynamics simulation of a graphite-supported copper nanocluster: thermodynamic properties and gas adsorption

Molecular dynamics simulations were conducted for a cubic Cu cluster supported on a graphite bilayer. The Sutten–Chen and Lennard–Jones potentials were used for metal–metal and metal–graphite interactions, respectively. Heating and cooling processes were performed by NVT simulations at different temperatures in the range 200 to 1800?K. The melting point was identified on the basis of caloric and heat capacity curves. The calculated melting point was 770?K, far below the bulk melting point of crystalline copper. Several phenomena such as the appearance of a hysteresis (irreversibility) in caloric curves, surface melting, and cluster-induced surface wetting were justified from the results. The simulation of cluster in the presence of gas atmosphere showed that the CO gas is adsorbed more than H₂ and it has a greater impact on the cluster's structure.