Molecular Cage Impregnated Palladium Nanoparticles: Efficient, Additive-Free Heterogeneous Catalysts for Cyanation of Aryl Halides

Two shape-persistent covalent cages (CC1(r) and CC2(r)) have been devised from triphenyl amine-based trialdehydes and cyclohexane diamine building blocks utilizing the dynamic imine chemistry followed by imine bond reduction. The cage compounds have been characterized by several spectroscopic techniques which suggest that CC1(r) and CC2(r) are 2+3] and 8+12] self-assembled architectures, respectively. These state-of-the-art molecules have a porous interior and stable aromatic backbone with multiple palladium binding sites to engineer the controlled synthesis and stabilization of ultrafine palladium nanoparticles (PdNPs). As-synthesized cage-embedded PdNPs have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and powder X-ray diffraction (PXRD). Inductively coupled plasma optical emission spectrometry reveals that Pd@CC1(r) and Pd@CC2(r) have 40 and 25 wt% palladium loading, respectively. On the basis of TEM analysis, it has been estimated that as small as similar to 1.8 nm PdNPs could be stabilized inside the CC1(r), while larger CC2(r) could stabilize similar to 3.7 nm NPs. In contrast, reduction of palladium salts in the absence of the cages form structure less agglomerates. The well-dispersed cage-embedded NPs exhibit efficient catalytic performance in the cyanation of aryl halides under heterogeneous, additive-free condition. Moreover, these materials have excellent stability and recyclability without any agglomeration of PdNPs after several cycles.

Chitosan Immobilized Porous Polyolefin As Sustainable and Efficient Antibacterial Membranes

Polyolefinic membranes have attracted a great deal of interest owing to their ease of processing and chemical inertness. In this study, porous polyolefin membranes were derived by selectively etching PEO from PE/PEO (polyethylene/poly(ethylene oxide)) blends. The hydrophobic polyolefin (low density polyethylene) was treated with UV-ozone followed by dip coating in chitosan acetate solution to obtain a hydrophilic-antibacterial surface. The chitosan immobilized PE membranes were further characterized by Fourier transform infrared spectroscope (FTIR) and X-ray photoelectron spectroscope (XPS). It was found that surface grafting of chitosan onto PE membranes enhanced the surface roughness and the concentration of nitrogen (or amine) scaled with increasing concentration of chitosan (0.25 to 2% wt/vol), as inferred from Kjeldahl nitrogen analysis. The pure water flux was almost similar for chitosan immobilized PE membranes as compared to membranes without chitosan. The bacterial population, substantially reduced for membranes with higher concentration of chitosan. For instance, 90 and 94% reduction in Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) colony forming unit respectively was observed with 2% wt/vol of chitosan. This study opens new avenues in designing polyolefinic based antibacterial membranes for water purification.

Engineering a multi-biofunctional composite using poly(ethylenimine) decorated graphene oxide for bone tissue regeneration

Toward preparing strong multi-biofunctional materials, poly(ethylenimine) (PEI) conjugated graphene oxide (GO_PEI) was synthesized using poly(acrylic acid) (PAA) as a spacer and incorporated in poly( e-caprolactone) (PCL) at different fractions. GO_PEI significantly promoted the proliferation and formation of focal adhesions in human mesenchymal stem cells (hMSCs) on PCL. GO_PEI was highly potent in inducing stem cell osteogenesis leading to near doubling of alkaline phosphatase expression and mineralization over neat PCL with 5% filler content and was approximate to 50% better than GO. Remarkably, 5% GO_ PEI was as potent as soluble osteoinductive factors. Increased adsorption of osteogenic factors due to the amine and oxygen containing functional groups on GO_ PEI augment stem cell differentiation. GO_ PEI was also highly efficient in imparting bactericidal activity with 85% reduction in counts of E. coli colonies compared to neat PCL at 5% filler content and was more than twice as efficient as GO. This may be attributed to the synergistic effect of the sharp edges of the particles along with the presence of the different chemical moieties. Thus, GO_ PEI based polymer composites can be utilized to prepare bioactive resorbable biomaterials as an alternative to using labile biomolecules for fabricating orthopedic devices for fracture fixation and tissue engineering.

A Deep-Blue Electroluminescent Device Based on a Coumarin Derivative

The design and synthesis is reported of 7-(9H-carbazol-9-yl)-4-methylcoumarin (Cz-Cm), comprising a carbazole donor moiety and a 4-methylcoumarin acceptor unit, for use in a blue organic light-emitting diode. A detailed solid state, theoretical and spectroscopic study was performed to understand the structure-property relationships. The material exhibits deep-blue emission and high photoluminescence quantum yield both in solution and in a doped matrix. A deep-blue electroluminescence emission at 430nm, a maximum brightness of 292cdm(-2) and an external quantum efficiency of 0.4% was achieved with a device configured as follows: ITO/NPD (30nm)/TCTA (20nm)/CzSi(10nm)/10wt% Cz-Cm:DPEPO (10nm)/TPBI (30nm)/LiF (1nm)/Al ITO=indium tin oxide, NPD=N,N-di(1-naphthyl)-N,N-diphenyl-(1,1-biphenyl)-4,4-diamine, TCTA=tris(4-carbazoyl-9-ylphenyl)amine, CzSi=9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole, DPEPO=bis2-(diphenylphosphino)phenyl]ether oxide, TPBI=1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene].