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Breaking Trade-Off between Selectivity and Activity of Nickel-Based Hydrogenation Catalysts by Tuning Both Steric Effect and d-Band Center.

ABSTRACT: For selective hydrogenation of chemicals the high selectivity is always at the expense of activity and improving both selectivity and activity is challenging. Here, by chelating with p-fluorothiophenol (SPhF)-arrays, both steric and electronic effects are created to boost the performance of cheap nickel-based catalysts. Compared with dinickel phosphide, the SPhF-chelated one exhibits nearly 12 times higher activity and especially its selectivity is increased from 38.1% and 21.3% to nearly 100% in hydrogenations of 3-nitrostyrene and cinnamaldehyde. Commercial catalysts like Raney Ni chelating with SPhF-array also exhibits an enhanced selectivity from 20.5% and 23.4% to ?100% along with doubled activity. Both experimental and density functional theory (DFT) calculation prove that the superior performance is attributed to the confined flat adsorption by ordered SPhF-arrays and downshifted d-band center of catalysts, leading to prohibited hydrogenation of the vinyl group and accelerative H₂ activation. Such a surface modification can provide an easily-realized and low-cost way to design catalysts for the selective hydrogenation.

SUBMITTER: Gao R

PROVIDER: S-EPMC6523378 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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Breaking Trade-Off between Selectivity and Activity of Nickel-Based Hydrogenation Catalysts by Tuning Both Steric Effect and d-Band Center.

Gao Ruijie R Pan Lun L Wang Huiwen H Yao Yunduo Y Zhang Xiangwen X Wang Li L Zou Ji-Jun JJ

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 20190325 10

For selective hydrogenation of chemicals the high selectivity is always at the expense of activity and improving both selectivity and activity is challenging. Here, by chelating with <i>p</i>-fluorothiophenol (SPhF)-arrays, both steric and electronic effects are created to boost the performance of cheap nickel-based catalysts. Compared with dinickel phosphide, the SPhF-chelated one exhibits nearly 12 times higher activity and especially its selectivity is increased from 38.1% and 21.3% to nearly ...[more]

PMID: 31131202

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Project description:BACKGROUND:Photoimmunotherapy involves targeted delivery of photosensitizers via an antibody conjugate (i.e., photoimmunoconjugate, PIC) followed by light activation for selective tumor killing. The trade-off between PIC selectivity and PIC uptake is a major drawback limiting the efficacy of photoimmunotherapy. Despite ample evidence showing that photoimmunotherapy is most effective when combined with chemotherapy, the design of nanocarriers to co-deliver PICs and chemotherapy drugs remains an unmet need. To overcome these challenges, we developed a novel photoimmunoconjugate-nanoliposome (PIC-Nal) comprising of three clinically used agents: anti-epidermal growth factor receptor (anti-EGFR) monoclonal antibody cetuximab (Cet), benzoporphyrin derivative (BPD) photosensitizer, and irinotecan (IRI) chemotherapy. RESULTS:The BPD photosensitizers were first tethered to Cet at a molar ratio of 6:1 using carbodiimide chemistry to form PICs. Conjugation of PICs onto nanoliposome irinotecan (Nal-IRI) was facilitated by copper-free click chemistry, which resulted in monodispersed PIC-Nal-IRI with an average size of 158.8?±?15.6 nm. PIC-Nal-IRI is highly selective against EGFR-overexpressing epithelial ovarian cancer cells with 2- to 6-fold less accumulation in low EGFR expressing cells. Successful coupling of PIC onto Nal-IRI enhanced PIC uptake and photoimmunotherapy efficacy by up to 30% in OVCAR-5 cells. Furthermore, PIC-Nal-IRI synergistically reduced cancer viability via a unique three-way mechanism (i.e., EGFR downregulation, mitochondrial depolarization, and DNA damage). CONCLUSION:It is increasingly evident that the most effective therapies for cancer will involve combination treatments that target multiple non-overlapping pathways while minimizing side effects. Nanotechnology combined with photochemistry provides a unique opportunity to simultaneously deliver and activate multiple drugs that target all major regions of a cancer cell-plasma membrane, cytoplasm, and nucleus. PIC-Nal-IRI offers a promising strategy to overcome the selectivity-uptake trade-off, improve photoimmunotherapy efficacy, and enable multi-tier cancer targeting. Controllable drug compartmentalization, easy surface modification, and high clinical relevance collectively make PIC-Nal-IRI extremely valuable and merits further investigations in living animals.

Dataset Information

Breaking Trade-Off between Selectivity and Activity of Nickel-Based Hydrogenation Catalysts by Tuning Both Steric Effect and d-Band Center.

Publications

Breaking Trade-Off between Selectivity and Activity of Nickel-Based Hydrogenation Catalysts by Tuning Both Steric Effect and d-Band Center.

Similar Datasets

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