Pd(II)-NHDC-Functionalized UiO-67 Type MOF for Catalyzing Heck Cross-Coupling and Intermolecular Benzyne-Benzyne-Alkene Insertion Reactions.

A novel palladium N-heterocyclic bis-carbene dicarboxylate ligand (Pd-NHDC-H2L) was successfully synthesized. In addition, an Pd-NHDC-containing UiO-67 type MOF (UiO-67-Pd-NHDC) was prepared on the basis of a size-matched ligand mixture of biphenyl-4,4'-dicarboxylic acid/Pd-NHDC-H2L (9/1) and ZrCl4 under solvothermal conditions. The obtained UiO-67-Pd-NHC MOF can be a highly heterogeneous catalyst to promote Heck cross-coupling and intermolecular benzyne-benzyne-alkene insertion reactions.

Dermal exposure to particle-bound polycyclic aromatic hydrocarbons from barbecue fume as impacted by physicochemical conditions.

Inhalation of size-dependent particle-bound polycyclic aromatic hydrocarbons (PAHs) has been extensively studied, whereas dermal absorption has not been adequately investigated. To address this knowledge gap, dermal absorption of size-dependent particle-bound PAHs was characterized through the collection of indoor air and forearm wipe samples in the setting of an indoor barbecue. The mass of size-fractioned PAHs associated with particulate matter was greater in fine particles (<1.8 µm) than in coarse particles (>1.8 µm). Gas-particle distribution of specific PAHs from barbecue fume was ascribed to both adsorption and absorption which would probably be close to equilibrium, while that from background air was dominated by absorption. Forearm-deposited amounts of particulate PAHs suggested that removal of coarse and fine particles could minimize exposure to low and high molecular-weight (MW) PAHs, respectively. Besides, the concentrations of particulate PAHs in forearms wipe were significantly correlated to their dry deposition fluxes with coarse particles, but weakly correlated to those with fine particles. This indicated that particle size would influence dermal absorption efficiency of particle-bound PAHs with fine particles prolonging dermal exposure to PAHs. Overall, higher MW particle-bound PAHs derived from barbecue fume may pose higher risk to human health by dermal absorption than lower MW PAHs.

Porous organic polymer with in situ generated palladium nanoparticles as a phase-transfer catalyst for Sonogashira cross-coupling reaction in water.

A new Pd nanoparticle loaded and imidazolium-ionic liquid decorated organic polymer of Pd@PTC-POP was readily fabricated via a Pd(PPh3)4 catalysed in situ one-pot Suzuki cross-coupling reaction between imidazolium attached dibromobenzene and 1,3,5-tri(4-pinacholatoborolanephenyl)benzene. Besides the high thermal and chemical stability, the obtained Pd@PTC-POP can be used as a highly active and reusable phase-transfer solid catalyst to promote the Sonogashira coupling reaction in water. The obtained results indicate that the Pd@PTC-POP herein could create a versatile family of solid phase transfer catalysts for promoting a broad scope of reactions carried out in water.

Nickel-metalated porous organic polymer for Suzuki-Miyaura cross-coupling reaction.

A new Ni(ii)-α-diimine-based porous organic polymer, namely Ni(ii)-α-diimine-POP, was constructed in high yield via the Sonogashira coupling reaction between the metallo-building block of Ni(ii)-α-diimine and 1,3,5-triethynylbenzene. Besides the high thermal and chemical stability, the obtained Ni(ii)-α-diimine-POP can be a highly active reusable heterogeneous catalyst to promote the Suzuki-Miyaura coupling reaction. The obtained results indicate that the Ni(ii)-α-diimine-POP herein is a promising sustainable alternative to the Pd-based catalysts for catalysing the C-C formation in a heterogeneous way.