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Cite this: J. Am. Chem. Soc. 2021, 143, 49, 20527–20528
Publication Date (Web):December 7, 2021

Copyright © 2021 American Chemical Society. This publication is available under these Terms of Use.

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Building a Better Ethylene Oligomerization Catalyst

Christen Brownlee
More than a million tons of linear alpha olefins, such as 1-butene, 1-hexene, and 1-octene, are produced annually as starting materials for polyethylene production. The conventional process that oligomerizes ethylene into these olefins uses a homogeneous nickel catalyst; however, researchers have recently begun exploring the use of nickel-functionalized metal–organic frameworks (MOF) designed with active sites to mimic the catalytic properties of the homogeneous nickel catalyst.
Laura Gagliardi, Aditya Bhan, and co-workers report a new member of this family: a nickel-functionalized UiO-66 MOF that, after an induction period, exhibits stable on-stream catalysis for >15 days without co-catalysts or initiators, properties that are unprecedented in framework or supported heterogeneous catalytic materials for ethylene oligomerization (DOI: 10.1021/jacs.1c09320). The researchers show that higher ethylene pressures shorten induction periods in this material and create more active sites. Further experiments show that ethylene oligomerization in this system is first order in ethylene pressure from 100 to 1800 kPa, with an activation energy of 81 kJ mol–1 at temperatures from 443 to 503 K. Thermodynamics analyses and density functional theory calculations suggest that this MOF facilitates ethylene oligomerization through a Cossee–Arlman mechanism. The authors suggest that these findings could help optimize the design of nickel-functionalized MOFs to provide stable and tunable platforms for catalytic ethylene oligomerization.

Thin and Large: Synthetic Strategy for Large-Area 2D Materials

Dalia Yablon, Ph.D.
Atomically thin two-dimensional (2D) materials such as graphene and boron nitride receive a lot of attention for their promise for next-generation electronic materials and new properties for optoelectronics. One limitation to their use is the ability to synthesize them in large lateral sizes in a defect-free manner. A team of chemists led by William Tisdale have now synthesized a new class of hybrid organic–inorganic 2D semiconductors in large microcrystals up to 1 mm in size with improved photoluminescence lifetime (DOI: 10.1021/jacs.1c09106).
The 2D material studied here is silver phenylselenolate (AgSePh), a 2D metal–organic chalcogenate (MOC) involving covalent interactions between its organic and inorganic components that promote its stability. The chemists improve the size and quality of its crystals by adding amines during the solution-phase growth reaction, reducing the complexity of the AgSePh synthesis to a single step using stable reagents. 77Se NMR spectroscopy elucidates the mechanism, revealing a dual role for amines in the synthesis. This strategy can be applied to synthesize other large-area 2D MOC materials for further fundamental studies and device integration.

One-Carbon Insertion Reaction Revolutionizes Carbon–Fluorine Bond Activation Chemistry

Kimberly Bolduc
Chemists often refer to atoms or moieties as “building blocks”, as if every molecule can be easily constructed of its constituent pieces like a child’s wooden block set. However, in reality, chemistry is more like a game of Tetris with all of the awkward pieces. Complete control over the constitution and conformation of molecules is the ultimate dream of synthetic organic chemistry. One starting point is carbon–fluorine bonds. These bonds are especially strong and give materials like PTFE amazing and useful properties. Activation of the C–F bond presents many opportunities for customization to produce new compounds.
Working toward this goal, Fei Wang, Yoshihiro Nishimoto, and Makoto Yasuda have achieved the diastereoselective insertion of a single carbon atom into the C–F bond of benzylic fluorides via diazo esters with BF3 as a catalyst (DOI: 10.1021/jacs.1c10517). Confirming their results with 1H NMR and 19F NMR, the researchers were able to find that their α-fluoro-α,β-diaryl esters products were created with a wide range of functional groups and in high yield. By synthesizing a fluoro analog of a transient receptor and potential canonical (TRPC) channel inhibitor, the researchers demonstrate that their reaction pathway could be used to create novel compounds with a wide range of applications including medicine, technology, and manufacturing.

Two Biomarkers Better Than One for Early Diagnosis of Acute Kidney Injury

Sarah Anderon
Acute kidney injury (AKI), a sudden loss of kidney function, can be caused by sepsis, hypotension, kidney stones and medicines such as the anti-cancer compound cisplatin. To identify drug toxicity and prevent severe kidney damage, AKI must be detected at an initial stage. However, current methods that rely on kidney imaging or changes in blood chemistry can only diagnose AKI in an advanced state.
Now, Deju Ye and colleagues report a kidney-clearable, near-infrared fluorescent probe that detects two biomarkers of the cellular apoptosis process underpinning AKI to facilitate early diagnosis (DOI: 10.1021/jacs.1c08898). Using a one-pot sequential click reaction, the researchers synthesized a probe that incorporates ligands that bind phosphatidylserine and a substrate for the caspase-3 enzyme, which generates a fluorophore when cleaved. The probe gave greater fluorescence intensity than a control molecule that targets only one biomarker, increasing signal-to-noise ratio. The team used the probe to detect cisplatin-induced AKI in mice, observing that fluorescence intensity correlated with caspase-3 activity as AKI progressed and that kidney injury could be detected after 24 h. The probe also tracked recovery of kidney function upon administration of the drug N-acetyl-l-cysteine, revealing that it can be used to screen AKI therapeutics. This work establishes a non-invasive strategy to visualize AKI in real time and may be adapted to monitor other conditions characterized by apoptosis.

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