The most fundamental concepts in chemistry are structure, energetics, reactivity and their inter-relationships, which are indispensable for promoting chemistry into a rational science. In this regard, bond energy, the intrinsic determinant directly related to structure and reactivity, should be most essential in serving as a quantitative basis for the design and understanding of organic transformations. Although C-H activation/functionalization have drawn tremendous research attention and flourished during the past decades, understanding the governing rules of bond energetics in these processes is still fragmentary and seems applicable only to limited cases, such as metal-oxo-mediated hydrogen atom abstraction. Despite the complexity of C-H activation/functionalization and the difficulties in measuring bond energies both for the substrates and intermediates, this is definitely a very important issue that should be more generally contemplated. To this end, this review is rooted in the energetic aspects of C-H activation/functionalization, which were previously rarely discussed in detail. Starting with a concise but necessary introduction of various classical methods for measuring heterolytic and homolytic energies for C-H bonds, the present review provides examples that applied the concept and values of C-H bond energy in rationalizing the observations associated with reactivity and/or selectivity in C-H activation/functionalization.
Afterglow imaging through the collection
of persistent luminescence
after the stopping of light excitation holds enormous promise for
advanced biomedical uses. However, efficient near-infrared (NIR)-emitting
afterglow luminescent materials and probes (particularly the organic
and polymeric ones) are still very limited, and their in-depth biomedical
applications such as precise image-guided cancer surgery are rarely
reported. Here, we design and synthesize a NIR afterglow luminescent
nanoparticle with aggregation-induced emission (AIE) characteristics
(named AGL AIE dots). It is demonstrated that the AGL AIE dots emit
rather-high NIR afterglow luminescence persisting over 10 days after
the stopping of a single excitation through a series of processes
occurring in the AIE dots, including singlet oxygen production by
AIE luminogens (AIEgens), Schaap’s dioxetane formation, chemiexcitation
by dioxetane decomposition, and energy transfer to NIR-emitting AIEgens.
The animal studies reveal that the AGL AIE dots have the innate property
of fast afterglow signal quenching in normal tissues, including the
liver, spleen, and kidney. After the intravenous injection of AGL
AIE dots into peritoneal carcinomatosis bearing mice, the tumor-to-liver
ratio of afterglow imaging is nearly 100-fold larger than that for
fluorescence imaging. The ultrahigh tumor-to-liver signal ratio, together
with low afterglow background noise, enables AGL AIE dots to give
excellent performance in precise image-guided cancer surgery.
Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative pollutants found in water resources at concentrations harmful to human health. Whereas current PFAS destruction strategies use nonselective destruction mechanisms, we found that perfluoroalkyl carboxylic acids (PFCAs) could be mineralized through a sodium hydroxide–mediated defluorination pathway. PFCA decarboxylation in polar aprotic solvents produced reactive perfluoroalkyl ion intermediates that degraded to fluoride ions (78 to ~100%) within 24 hours. The carbon-containing intermediates and products were inconsistent with oft-proposed one-carbon-chain shortening mechanisms, and we instead computationally identified pathways consistent with many experiments. Degradation was also observed for branched perfluoroalkyl ether carboxylic acids and might be extended to degrade other PFAS classes as methods to activate their polar headgroups are identified.
We report an ambimodal trispericyclic transition state leading to [6+4]-, [4+6]-, and [8+2]cycloadducts in the reactions of 8,8-disubstituted heptafulvenes with 6,6-dimethylfulvene. The potential energy surfaces for these reactions were explored with ωB97X-D density functional theory. Quasi-classical direct molecular dynamics simulations gave information on the ratios of products expected in these reactions.Communication pubs.acs.org/JACS
Transfer of electrophilic NH to sulfides and a subsequent sulfimine‐promoted fast O transfer have been achieved in a one‐pot process unprecedentedly for the preparation of sulfoximines at ambient temperature under air. The transformations, which are metal‐, ligand‐, base‐, additive‐free, and operationally simple, proceed in just 5 min and furnish NH‐sulfoximines in good‐to‐excellent yields (up to 99 %) by treatment of sulfides with a combination of PhI(OAc)2 and ammonia source. A variety of commercially available and inexpensive electrophilic nitrogen sources are successfully used in the oxidative sulfide‐to‐sulfoximine conversions. This method features a high efficiency, excellent functional‐group tolerance, and broad substrate scope, which may facilitate its applications in medicinal chemistry area.
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