Angewandte Chemie International Edition

Ponder, James F.; Gregory, Shawn A.; Atassi, Amalie; Advincula, Abigail A.; Rinehart, Joshua M.; Freychet, Guillaume; Su, Gregory M.; Yee, Shannon K.; Reynolds, John R.

doi: 10.1002/anie.202211600pmid: 36269867

Herein, a route to produce highly electrically conductive doped hydroxymethyl functionalized poly(3,4‐ethylenedioxythiophene) (PEDOT) films, termed PEDOT(OH) with metal‐like charge transport properties using a fully solution processable precursor polymer is reported. This is achieved via an ester‐functionalized PEDOT derivative [PEDOT(EHE)] that is soluble in a range of solvents with excellent film‐forming ability. PEDOT(EHE) demonstrates moderate electrical conductivities of 20–60 S cm−1 and hopping‐like (i.e., thermally activated) transport when doped with ferric tosylate (FeTos3). Upon basic hydrolysis of PEDOT(EHE) films, the electrically insulative side chains are cleaved and washed from the polymer film, leaving a densified film of PEDOT(OH). These films, when optimally doped, reach electrical conductivities of ≈1200 S cm−1 and demonstrate metal‐like (i.e., thermally deactivated and band‐like) transport properties and high stability at comparable doping levels.

Li, Ang; Zhang, Yuyan; Heard, Christopher J.; Gołąbek, Kinga; Ju, Xiaohui; Čejka, Jiří; Mazur, Michal

doi: 10.1002/anie.202213361pmid: 36342499

Supported metal nanoparticles are used as heterogeneous catalysts but often deactivated due to sintering at high temperatures. Confining metal species into a porous matrix reduces sintering, yet supports rarely provide additional stabilization. Here, we used the silanol‐rich layered zeolite IPC‐1P to stabilize ultra‐small Rh nanoparticles. By adjusting the IPC‐1P interlayer space through swelling, we prepared various architectures, including microporous and disordered mesoporous. In situ scanning transmission electron microscopy confirmed that Rh nanoparticles are resistant to sintering at high temperature (750 °C, 6 hrs). Rh clusters strongly bind to surface silanol quadruplets at IPC‐1P layers by hydrogen transfer to clusters, while high silanol density hinders their migration based on density functional theory calculations. Ultimately, combining swelling with long‐chain surfactant and utilizing metal‐silanol interactions resulted in a novel, catalytically active material—Rh@IPC_C22.

Zhang, Wen‐Wen; Li, Bi‐Jie

doi: 10.1002/anie.202214534pmid: 36344453

Despite the advances in the area of catalytic alkene hydrosilylation, the enantioselective hydrosilylation of alkenes bearing a heteroatom substituent is scarce. Here we report a rhodium‐catalyzed hydrosilylation of β,β‐disubstituted enamides to directly afford valuable α‐aminosilanes in a highly regio‐, diastereo‐, and enantioselective manner. Stereodivergent synthesis could be achieved by regulating substrate geometry and ligand configuration to generate all the possible stereoisomers in high enantio‐purity.

Ma, Wenjie; Wu, Hongxiang; Liu, Sha; Wei, Tongyao; Li, Xiang David; Liu, Han; Li, Xuechen

doi: 10.1002/anie.202214053pmid: 36344442

Chemical synthesis of proteins bearing base‐labile post‐translational modifications (PTMs) is a challenging task. For instance, O‐acetylation and S‐palmitoylation PTMs cannot survive Fmoc removal conditions during Fmoc‐solid phase peptide synthesis (SPPS). In this work, we developed a new Boc‐SPPS‐based strategy for the synthesis of peptide C‐terminal salicylaldehyde (SAL) esters, which are the key reaction partner in Ser/Thr ligation and Cys/Pen ligation. The strategy utilized the semicarbazone‐modified aminomethyl (AM) resin, which could support the Boc‐SPPS and release the peptide SAL ester upon treatment with TFA/H2O and pyruvic acid. The non‐oxidative aldehyde regeneration was fully compatible with all the canonical amino acids. Armed with this strategy, we finished the syntheses of the O‐acetylated protein histone H3(S10ac, T22ac) and the hydrophobic S‐palmitoylated peptide derived from caveolin‐1.

Zhu, Miao; Zhou, Qin; Cheng, He; Sha, Ye; Bregadze, Vladimir I.; Yan, Hong; Sun, Zhe; Li, Xiang

doi: 10.1002/anie.202213470pmid: 36203221

The combination of carbon‐based nanohoops with other functional organic molecular structures should lead to the design of new molecular configurations with interesting properties. Here, necklace‐like nanohoops embedded with carborane were synthesized for the first time. The unique deboronization of o‐carborane has led to the facile preparation of ionic nanohoop compounds. Nanohoops functionalized by nido‐o‐carborane show excellent fluorescence emission, with a solution quantum yield of up to 90.0 % in THF and a solid‐state quantum efficiency of 87.3 %, which opens an avenue for the applications of the nanohoops in OLEDs and bioimaging.

Yan, Rui; Zhao, Zhenyang; Cheng, Menghao; Yang, Zhao; Cheng, Chong; Liu, Xikui; Yin, Bo; Li, Shuang

doi: 10.1002/anie.202215414pmid: 36321878

Accelerating insoluble Li2S2−Li2S reduction catalysis to mitigate the shuttle effect has emerged as an innovative paradigm for high‐efficient lithium‐sulfur battery cathodes, such as single‐atom catalysts by offering high‐density active sites to realize in situ reaction with solid Li2S2. However, the profound origin of diverse single‐atom species on solid‐solid sulfur reduction catalysis and modulation principles remains ambiguous. Here we disclose the fundamental origin of Li2S2−Li2S reduction catalysis in ferromagnetic elements‐based single‐atom materials to be from their spin density and magnetic moments. The experimental and theoretical studies disclose that the Fe−N4‐based cathodes exhibit the fastest deposition kinetics of Li2S (226 mAh g−1) and the lowest thermodynamic energy barriers (0.56 eV). We believe that the accelerated Li2S2−Li2S reduction catalysis enabled via spin polarization of ferromagnetic atoms provides practical opportunities towards long‐life batteries.

Harabuchi, Yu; Hayashi, Hiroki; Takano, Hideaki; Mita, Tsuyoshi; Maeda, Satoshi

doi: 10.1002/anie.202217392pmid: N/A

Ahlburg, Nils L.; Hergert, Oliver; Jones, Peter G.; Werz, Daniel B.

doi: 10.1002/anie.202214390pmid: 36322458

A novel class of highly activated donor‐acceptor cyclopropanes bearing only a single, vinylogous acceptor is presented. These strained moieties readily undergo cycloadditions with aldehydes, ketones, thioketones, nitriles, naphth‐2‐ols and various other substrates to yield the corresponding carbo‐ and heterocycles. Diastereocontrol can be achieved through the choice of catalyst (Brønsted or Lewis acid). The formation of tetrahydrofurans was shown to be highly enantiospecific when chiral cyclopropanes are employed. A series of mechanistic and kinetic experiments was conducted to elucidate a plausible catalytic cycle and to rationalize the stereochemical outcome.

Li, Xianbao; Li, Qi; Wu, Aoli; Li, Junbai

doi: 10.1002/anie.202214184pmid: 36336663

Control of symmetry breaking of materials provides large opportunities to regulate their properties and functions. Herein, we report breaking the symmetry of layered dipeptide crystals by utilizing CO2 to induce the adjacent monomolecular layers to stack from the opposite to the same direction. The role of CO2 is to cover the interlayer interaction sites and force the dipeptides to adsorb at asymmetric positions. Further, the dipeptide crystals exhibit far superior piezoelectricity after symmetry breaking and the piezoelectric voltage generated from the dipeptide‐based generators becomes more than 500 % higher than before. This work reveals a potential route to engineer structures and properties of layered materials and provides a deep insight into the control of non‐covalent interactions.

Zhang, Xiaoyu; Hu, Zhenyu; Sun, Qi; Liang, Xing; Gu, Puzhong; Huang, Jia; Zu, Guoqing

doi: 10.1002/anie.202213952pmid: 36346155

Broad‐range‐response pressure‐sensitive wearable electronics are urgently needed but their preparation remains a challenge. Herein, we report unprecedented bioinspired wearable electronics based on stretchable and superelastic reduced graphene oxide/polyurethane nanocomposite aerogels with gradient porous structures by a sol‐gel/hot pressing/freeze casting/ambient pressure drying strategy. The gradient structure with a hot‐pressed layer promotes strain transfer and resistance variation under high pressures, leading to an ultrabroad detection range of 1 Pa–12.6 MPa, one of the broadest ranges ever reported. They can withstand 10 000 compression cycles under 1 MPa, which can't be achieved by traditional flexible pressure sensors. They can be applied for broad‐range‐response electronic skins and monitoring various physical signals/motions and ultrahigh pressures of automobile tires. Moreover, the gradient aerogels can be used as high‐efficient gradient separators for water purification.