Journal of the American Chemical Society最新文献

An effective route to diameter-controlled single-walled carbon nanotubes (SWCNTs) remains elusive. The use of organic templates to precisely control the diameter of the resulting nanotubes holds great promise in this regard but has hitherto had very limited practical success. A main obstacle is the limited availability of suitable organic templates. Here, we report the diameter-controlled bottom-up synthesis of SWCNTs with elaborately designed [2n]collarenes, hydrocarbon belts consisting of alternating phenylene and 1,4-cyclohexadiene rings, as rigid organic templates. A new approach has been developed to construct these collarenes, which are then used as templates in the bottom-up growth of SWCNTs. The resulting SWCNTs exhibit narrow diameter distributions, matching the diameters of the employed collarene templates. This work greatly propels the synthesis of diameter-controlled SWCNTs.

Global iodine emissions have been increasing rapidly in recent decades, further influencing the Earth's climate and human health. However, our incomplete understanding of the iodine chemical cycle, especially the fate of higher iodine oxides, introduces substantial uncertainties into atmospheric modeling. I₂O₃ was previously deemed a "dead end" in iodine chemistry; however, we provide atomic-level evidence that I₂O₃ can undergo rapid air-water or air-ice interfacial reactions within several picoseconds; these reactions are facilitated by prevalent chemicals on seawater such as amines and halide ions, to produce photolabile reactive iodine species such as HOI and IX (X = I, Br, and Cl). The heterogeneous chemistry of I₂O₃ leads to the rapid formation of iodate ions (IO₃^-), which is the predominant soluble iodine and its concentration cannot be well explained by current chemistry. These new loss pathways for atmospheric I₂O₃ can further explain its absence in field observations and its presence in laboratory experiments; furthermore, these pathways represent a heterogeneous recycling mechanism that can activate the release of reactive iodine from oceans, polar ice/snowpack, or aerosols. Rapid reactive adsorption of I₂O₃ can also promote the growth of marine aerosols. These findings provide novel insights into iodine geochemical cycling.

Nature chooses a high-valent tungsten center at the active site of the enzyme acetylene hydratase to facilitate acetylene hydration to acetaldehyde. However, the reactions of tungsten-coordinated acetylene are still not well understood, which prevents the development of sustainable bioinspired alkyne hydration catalysts. Here we report the reactivity of two bioinspired tungsten complexes with the acetylene ligand acting as a four-: [W(CO)(C₂H₂)(PymS)₂] (1) and a two-electron donor: [WO(C₂H₂)(PymS)₂] (3), with PMe₃ as a nucleophile to simulate the enzyme's reactivity (PymS = 4-(trifluoromethyl)-6-methylpyrimidine-2-thiolate). In dichloromethane, compound 1 was found to react to the cationic carbyne [W≡CCH₂PMe₃(CO)(PMe₃)₂(PymS)]Cl (2-Cl) while 3 reacts to the vinyl compound [WO(CH═CHPMe₃)(PMe₃)₃(PymS)]Cl (4-Cl). The formation of the latter follows the common rules applied to η²-alkyne complexes, whereas the carbyne formation was not expected due to the challenging 1,2-H shift. To understand these differences in behavior between seemingly similar acetylene complexes, stepwise addition of the nucleophile in various solvents was investigated by synthetic, spectroscopic, and computational approaches. In this manuscript, we describe that only a four-electron donor acetylene complex can react to the carbyne over the η¹-vinyl intermediate and that 1,2-H shift can be assisted by an H-transfer reagent (in this case, the decoordinated PymS ligand). Furthermore, to favor the attack of PMe₃ at W coordinated acetylene, the metal center needs to be electron-poor and crowded enough to prevent nucleophile coordination. Finally, the intricate role of the anionic PymS ligand in the vicinity of the first coordination sphere models the potential involvement of amino acid residues during acetylene transformations in AH.

Acetonitrile (CH₃CN) is considered a very stable molecule in aqueous solutions, and its deprotonation to produce strongly basic ^-CH₂CN requires harsh conditions. CH₃CN is also present in the atmosphere, but its chemical transformation pathway at the air-water interface is unknown. In this study, we discovered and verified the unprecedented spontaneous generation of ^-CH₂CN from the CH₃CN-H₂O solution at the air-water interface of microdroplets, and revealed the indirect deprotonation mechanism of CH₃CN by synergistic redox of ^•OH and electrons in the microdroplets through the capture of key intermediates and computational chemistry. In addition, the dynamic process of indirect deprotonation-protonation was also observed. The high reactivity of ^-CH₂CN in the droplets was revealed via nucleophilic addition to acetone, benzaldehyde, and the parent CH₃CN molecule. Furthermore, the ^-CH₂CN generated in the microdroplets underwent a barrier-free nucleophilic addition reaction with CO₂ to produce 2-cyanoacetic acid for CO₂ fixation. The synergistic redox reaction process revealed in this study provides new insights into microdroplet chemistry, and the distinctive CH₃CN reactions identified may provide new clues to unravel the mystery of the CH₃CN transformation in the atmospheric environment.

Surface modification through the formation of a self-assembled monolayer (SAM) can effectively engineer the physicochemical properties of the surface/material. However, the precise design of multifunctional SAMs at the molecular level is still a major challenge. Here, we jointly use N-heterocyclic carbenes (NHCs) and thiols to form multifunctional hetero-SAM systems that demonstrate excellent chemical stability, electrical conductivity, and, in silico, catalytic activity. This synergistic effect is facilitated by the high surface mobility and electron-rich nature of NHCs, combined with the strong binding strength of thiols. Scanning tunneling microscopy, electrical conductivity, and scanning electron microscope measurements, as well as density functional theory calculations, were employed to explore the synergistic interactions in the supramolecular SAMs. The van der Waals integration of ballbot-type NHCs and thiols enables the SAMs to exhibit both superior surface anticorrosion properties (attributing to the shift in the d-band center) and low surface resistance originating from the band alignment. Moreover, we find that the deposition sequence of flat-lying NHCs and thiols results in SAMs with different configurations, which can further tune the mechanistic pathway in silico in the acetylene hydrogenation process. Our results provide essential molecular insights into the local electronic control of the new SAM/metal interface and the high stability of the emergent multifunctionality (NHC/thiol)-SAMs forming self-assembled lamellae structures in the nanometer regime.

Organic ferroelectrics show great applications in the fields of biomedicine, including disease treatment, biosensors, and tissue engineering. Organosilicon pharmaceutical intermediates generally include chiral centers and have satisfying biosafety, biocompatibility, or even biodegradability, which provide versatile platforms for the design of ferroelectricity. However, their academic values in ferroelectricity have long been long overlooked. Here, we demonstrated the ferroelectric properties of 4-acetoxy-azacyclic butanone (4-AA), a key synthetic organosilicon-based intermediate of carbapenem drugs. This compound undergoes a 222F2-type ferroelectric-ferroelastic phase transition at 326 K. As an organic piezoelectric material, 4-AA can produce reactive oxygen species when subjected to ultrasonic vibrations. Combined with its desirable biocompatibility, this material may contribute to antimicrobial and wound healing, tumor treatment, etc. This work will provide inspiration for the discovery of multifunctional biomedical ferroelectric materials as well as their related application prospects.

Polyketide synthases (PKSs) are renowned for the structural diversity of the polyketide natural products they produce, but sulfur-containing functionalities are rarely installed by PKSs. We previously characterized thiocysteine lyase (SH) domains involved in the biosynthesis of the leinamycin (LNM) family of natural products, exemplified by LnmJ-SH and guangnanmycin (GnmT-SH). Here we report a detailed investigation into the PLP-dependent reaction catalyzed by the SH domains, guided by a 1.8 Å resolution crystal structure of GnmT-SH. A series of elaborate substrate mimics were synthesized to answer specific questions garnered from the crystal structure and from the biosynthetic logic of the LNM family of natural products. Through a combination of bioinformatics, molecular modeling, in vitro assays, and mutagenesis, we have developed a detailed model of acyl carrier protein (ACP)-tethered substrate-SH, and interdomain interactions, that contribute to the observed substrate specificity. Comparison of the GnmT-SH structure with archetypical PLP-dependent enzyme structures revealed how Nature, via evolution, has modified a common protein structural motif to accommodate an ACP-tethered substrate, which is significantly larger than any of those previously characterized. Overall, this study demonstrates how PLP-dependent chemistry can be incorporated into the context of PKS assembly lines and sets the stage for engineering PKSs to produce sulfur-containing polyketides.

The precise asymmetric photochemical transformation of organic compounds containing multiple reactive sites presents significant progress in synthetic chemistry. Herein, we report an unprecedented visible-light-induced cascade transformation of tropolone cyclic triene derivatives by using chiral photoactive metal-organic cages (cPMOCs) as enzyme-mimicking multipocket photocatalysts. The cage-confined photocatalysis promotes three successive elementary steps, i.e., enantioselective [2 + 2] photocycloaddition with chalcone, regio-, and diastereoselective α-ketol rearrangement, and a stereoselective 1,3-acyl shift, resulting in bicyclo[3.2.2]nonane skeleton with multichiral-centers unattainable by other methods. This study demonstrates how complex synthetic challenges of peri-, chemo-, and stereoselectivities could be subtly manipulated by cage-confined supramolecular catalysis for exploration of new reactivities.

The interaction between a solid and water at their interface, especially proton transfer, impacts molecular-scale catalysis, macroscopic environmental science, and geoscience. Although being highly desired, directly probing proton transfer between a solid and water is a great challenge, given the subnanometer to nanometer scale of the interface. The fundamental challenge lies in the lack of a measurement tool to sensitively observe local proton concentration without introducing an exogenous electrode or nanoparticle with a minimum size of tens of nanometers. Here, we demonstrate an azo-enhanced Raman scattering strategy to design a 2 nm long small-molecule pH probe with a chelating group anchoring to the solid surface. Empowered by the intramolecular Raman enhancing sensitivity, the probe directly observes proton transfer between water and nanoscale zero-valent iron (nZVI), a famous environmental material for pollution control. This molecular-scale interfacial probing methodology offers a powerful tool to pave the way for advanced environmental and geochemical discernment and management.