Search

• Palladium nanoparticles favour over-hydrogenation in butyne hydrogenation. • In contrast, palladium sulfide catalyst is highly selectivity for butyne hydrogenation. • Pd 4 S offers greater than 90% alkene selectivity for both but-1-yne & but-2-yne as reactants. • DFT calculations show desorption of alkene is more favourable than hydrogenation. The partial hydrogenation of but-1-yne and but-2-yne was studied with a view to probing the difference between external and internal alkynes. Catalysts with Pd and Pd 4 S active phases were prepared on a carbon nanofiber support. Over the simple Pd catalyst over-hydrogenation was common which restricted alkene selectivity greatly – 25–35% depending on temperature. In contrast, the Pd 4 S active phase offered exceptional alkene selectivity (maximum of 92–93% alkene selectivity for both the external and internal alkyne). DFT calculations were subsequently used to rationalise this difference in product selectivity – sulfur appears to change the geometry of the active site in Pd 4 S and create a surface which favours alkene desorption relative to over-hydrogenation. This work further emphases the potential of palladium sulfide phases as an alternative to purely metallic palladium catalysts for partial alkyne hydrogenation. [ABSTRACT FROM AUTHOR]

A biocompatible Bi@mSiO 2 @MnO 2 nanocomposite is fabricated using a facile stepwise reaction method, which exhibits powerful theranostic performance for CT/MR imaging-guided enhanced PTT/CDT/chemotherapy of tumours. [Display omitted] Cancer is a leading cause of death worldwide and seriously threatens the health of humans. The current clinical treatments for cancer are not efficient and always lead to significant side effects. Herein, a biocompatible and powerful theranostic agent (Bi@mSiO 2 @MnO 2 /DOX) is fabricated using a facile stepwise reaction method. The Bi nanoparticles (NPs) are coated by mesoporous silica to protect the Bi NPs from oxidation, which guarantees the stable photothermal effect of the Bi NPs. When the Bi@mSiO 2 @MnO 2 /DOX nanocomposites (NCs) accumulate in the tumour site, hyperthermia is generated by Bi NPs under near-infrared (NIR) light irradiation for photothermal therapy (PTT), and the generated heat triggers the release of DOX for chemotherapy in the tumour. In addition, the MnO 2 of the NCs responsively catalyses endogenous H 2 O 2 to generate O 2 , raising the oxygen level to enhance the effect of chemotherapy in the tumour microenvironment (TME), and consumes glutathione (GSH) to produce Mn2+ for magnetic resonance (MR) imaging. Under acidic TME conditions, H 2 O 2 and Mn2+ also produce toxic hydroxyl radical (· OH) for chemodynamic therapy (CDT). Furthermore, the Bi NPs can also be used as excellent contrast agents for X-ray computed tomography (CT) imaging of tumours with a high CT value (6.865 HU mM−1). The Bi@mSiO 2 @MnO 2 /DOX NCs exhibit a powerful theranostic performance for CT/MR imaging-guided enhanced PTT/CDT/chemotherapy, which opens a new prospect to rationally design theranostic agents for tumour imaging. [ABSTRACT FROM AUTHOR]