Ultrafast photoactivation of C─H bonds inside water-soluble nanocages

Science Advances
Ankita DasJyotishman Dasgupta

Abstract

Light energy absorbed by molecules can be harnessed to activate chemical bonds with extraordinary speed. However, excitation energy redistribution within various molecular degrees of freedom prohibits bond-selective chemistry. Inspired by enzymes, we devised a new photocatalytic scheme that preorganizes and polarizes target chemical bonds inside water-soluble cationic nanocavities to engineer selective functionalization. Specifically, we present a route to photoactivate weakly polarized sp3 C─H bonds in water via host-guest charge transfer and control its reactivity with aerial O2. Electron-rich aromatic hydrocarbons self-organize inside redox complementary supramolecular cavities to form photoactivatable host-guest charge transfer complexes in water. An ultrafast C─H bond cleavage within ~10 to 400 ps is triggered by visible-light excitation, through a cage-assisted and solvent water-assisted proton-coupled electron transfer reaction. The confinement prolongs the lifetime of the carbon-centered radical to enable a facile yet selective reaction with molecular O2 leading to photocatalytic turnover of oxidized products in water.

References

Jan 1, 1976·Proceedings of the National Academy of Sciences of the United States of America·R MathiesL Stryer
Oct 1, 1987·Applied Biochemistry and Biotechnology·R J Linhardt
Apr 2, 1998·Science·R N Zare
Feb 6, 1999·Annual Review of Physical Chemistry·R I Cukier, D G Nocera
Feb 19, 2002·Chemical Reviews·Ronald Breslow, Steven D. Dong
Feb 20, 2002·Chemical Reviews·Alexander E. Shilov, Georgiy B. Shul'pin
May 1, 2004·Annual Review of Physical Chemistry·James M Mayer
Jul 30, 2004·Journal of the American Chemical Society·Michito YoshizawaMakoto Fujita
Apr 20, 2005·Accounts of Chemical Research·Dorothea FiedlerKenneth N Raymond
Aug 12, 2005·Chemical Reviews·Jacopo TomasiRoberto Cammi
Dec 7, 2007·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Ive HermansPierre A Jacobs
Sep 19, 2008·Nature·Lawrence Que, William B Tolman
Sep 22, 2010·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Maria SaltaKeith R Stokes
Feb 8, 2011·Chemical Society Reviews·Will R Gutekunst, Phil S Baran
Oct 25, 2011·Accounts of Chemical Research·Tobias BrücklPhil S Baran
Apr 10, 2012·Accounts of Chemical Research·Brian G HashiguchiRoy A Periana
Sep 18, 2013·The Journal of Physical Chemistry. B·Ajay JhaJyotishman Dasgupta
Dec 3, 2013·Chemical Society Reviews·Cheng Yang, Yoshihisa Inoue
Dec 25, 2013·Chemical Society Reviews·Matthieu RaynalPiet W N M van Leeuwen
Jan 30, 2014·PloS One·Vasundhara PaliwalHemant J Purohit
Oct 22, 2014·Journal of the American Chemical Society·Rahul GeraJyotishman Dasgupta
Feb 24, 2015·Nature Chemistry·Q Zhang, K Tiefenbacher
Mar 6, 2015·Biochemistry·Jeffrey J Warren, James M Mayer
Aug 21, 2015·Nature Chemistry·Lutz Ackermann, Jie Li
Feb 23, 2017·The Journal of Physical Chemistry. B·Samuel H SchneiderSteven G Boxer
Apr 5, 2017·Annual Review of Biochemistry·Stephen D Fried, Steven G Boxer
May 16, 2017·The Journal of Physical Chemistry. a·Aditi Bhattacherjee, Sanjay Wategaonkar
May 18, 2017·Chemical Communications : Chem Comm·Kundan K Singh, Sayam Sen Gupta

❮ Previous
Next ❯

Citations

Feb 20, 2021·ACS Nano·Douglas G MontjoyNicholas A Kotov
Apr 23, 2021·Physical Chemistry Chemical Physics : PCCP·Rahul Gera, Jyotishman Dasgupta
Jun 30, 2019·Journal of the American Chemical Society·Karsten Heyne, Oliver Kühn
Aug 18, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Hemen GogoiAnindya Datta
Jan 28, 2022·Chemical Communications : Chem Comm·Rui WangYang Yu

❮ Previous
Next ❯

Methods Mentioned

BETA
NMR
PCET
Raman
column chromatography

Software Mentioned

Glotaran
Surface Xplorer
IGOR Pro
Gaussian

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.

Related Papers

Journal of the American Chemical Society
Rahul GeraJyotishman Dasgupta
Chemical Reviews
David R WeinbergThomas J Meyer
Chemical Reviews
My Hang V Huynh, Thomas J Meyer
© 2022 Meta ULC. All rights reserved