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Spotlights on Recent JACS Publications, Volume 145, Issue 32
Cite This: J. Am. Chem. Soc. 2023, 145, 17495−17496
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■ CONTROLLING GENES WITH PRECISION
Gene therapy promises to treat genetic disorders at their root
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cause�offering personalized treatments for a wide range of
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diseases. But for such therapies to be usable, they must be
extremely precise, targeting the disease-causing gene and no
other genes. This precision has proven to be a challenge.
Now, Jian-Hui Jiang, Zhenkun Wu, and co-workers have
progressed toward a solution by developing a strategy that
targets genes using synthetically engineered DNA with
catalytic properties, known as DNAzymes (DOI: 10.1021/
jacs.3c05413). These remarkable molecules allow precise
silencing of genes by targeting specific mRNA molecules
within living cells. By attaching specific chemical groups, the
genes can be effectively deactivated, and their activity can be
fully restored on-demand through a reaction triggered by
phosphine. Further adding to its versatility, the researchers
introduced controls using light and internal signals, enabling
precise on−off switching within the body.
In a compelling proof-of-concept experiment, the team
successfully silenced a gene associated with breast cancer in a
mouse model using their DNAzyme, which resulted in slowed
tumor growth. This research offers exciting possibilities for
more precise and personalized medical interventions in the
future, potentially revolutionizing disease treatment at the
genomic level through innovative strategies in gene regulation
and targeted therapies.
Kelly Montgomery
■ DETERMINING TORSION ANGLES IN TADF
EMITTERS
Organic light-emitting diodes (OLEDs)�a technology that
uses LEDs in which light is produced by organic molecules�
are used to create digital displays in devices such as television
screens and computer monitors, including portable systems
such as smartphones and hand-held game consoles. These
displays are made by placing a series of organic thin films
between two conductors, and then, when an electrical current
is applied, a bright light is emitted.
The organic molecules utilized by OLED technology are
generally π-conjugated materials: one such family of these
materials includes thermally activated delayed fluorescent
(TADF) systems. The torsion angle between the donor and
acceptor sections of a TADF molecule is one of the most
important factors in determining the performance of a TADF-
based OLED. However, the torsion angle is difficult to analyze
as organic molecules are in an amorphous state within OLEDs.
Now, Katsuaki Suzuki and Hironori Kaji have used dynamic
nuclear polarization enhanced solid-state nuclear magnetic
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resonance analysis to determine the torsion angle of a TADF
emitter (DOI: 10.1021/jacs.3c05204). The researchers were
able to experimentally determine the torsion angle of the
TADF emitter DACT-II, which possesses a diphenylamino
carbazole donor and a triphenyltriazine acceptor, to be 52°,
which is very close to that of the computer-simulated structure
in the gas phase (51°). This simple and efficient method can
be routinely used to determine torsion angles of TADF
emitters as well as other functional organic solids, including
optoelectronic materials.
Aisha N. Bismillah Ph.D.
■ ROLE OF SECOND COORDINATION SPHERE
ACIDITY REVEALED IN CO2 REDUCTION
CATALYSTS
Molecular catalysts have played a pivotal role in efforts toward
efficient electrochemical CO2 reduction. While CO2 has
enormous potential as a cheap and plentiful feedstock for
producing value added chemicals, there are a variety of kinetic
and thermodynamic hurdles for rapid and selective reduction.
Commonly used transition metal complexes are active toward
electrochemical reduction of CO2, but research to improve
these systems via modifying the primary coordination is
restricted by a balance of kinetics and the resulting
overpotential. To overcome limitations of primary sphere
modification, bio-inspired efforts have been explored utilizing
protic functionalities in the secondary coordination sphere
(SCS) in conjunction with an exogenous acid. Modification of
the SCS is capable of altering the kinetics, thermodynamics,
and reaction mechanisms; however, the relationship between
the catalytic performance and acidity of the SCS and
exogenous acid is not well understood.
Eva Nichols and co-workers have carried out careful work to
resolve the influence of SCS pKa and acidity of exogenous acids
on the driving forces of proton-transfer scenarios of catalytic
CO2 reduction (DOI: 10.1021/jacs.3c03919). The team
reports that the catalytic rate constant can be changed by
nearly an order of magnitude with just a 2-unit change in the
pKa of either the SCS or exogenous acid. Additionally, it is
determined that a less acidic SCS enforces more-ordered
transition states and lower enthalpic barriers, which the authors
Published: August 8, 2023
https://doi.org/10.1021/jacs.3c08566
J. Am. Chem. Soc. 2023, 145, 17495−17496
Journal of the American Chemical Society pubs.acs.org/JACS Spotlight

suggest may be due to variable solvation. This work

demonstrates how the modification of both the SCS and
exogenous acid pKa provides additional avenues in the rational
design of countless electrocatalytic systems.
Peter Rudd

■ ChatGPT: A NEW TOOL FOR CHEMISTS?

ChatGPT has made headlines around the world recently, as
the generative text algorithm, which uses a large language
model that ingests huge amounts of text, has proven able to
create uncannily realistic responses to human queries in a
variety of domains. Several web search engines have begun
using such large language, generative text programs to improve
the accuracy and readability of their search results. Could such
an approach work for searching the scientific literature in
chemistry?
A team of researchers led by Omar Yaghi think so (DOI:
10.1021/jacs.3c05819). The researchers presented a sample
for using ChatGPT in the application of artificial intelligence in
chemical research dealing with metal−organic frameworks.
More specifically, they have shown that ChatGPT can be used
for identifying research papers that cover specific research
areas. This simplifies research in looking for papers that cover a
specific topic, reducing the number of research papers that
have to be identified about a specific subject. In a text mining
sample, the research in the process used parsing, searching,
filtering, classification, summarization, and data unification,
identifying about 800 papers from a sample of about 26,000
papers. The research sets a foundation for further exploration
and application of large language modeling across various
scientific domains, opening a way for a new era of artificial-
intelligence-assisted chemistry research.
Alexander Hellemans

17496 https://doi.org/10.1021/jacs.3c08566
J. Am. Chem. Soc. 2023, 145, 17495−17496