Search Results - "Angewandte Chemie Vol. 134, No. 6 ( 2022-02)"

Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

In eukaryotic cells, enzymes are compartmentalized into specific organelles so that different reactions and processes can be performed efficiently and with a high degree of control. In this work, we show that these features can be artificially emulated in robust synthetic organelles constructed using an enzyme co‐compartmentalization strategy. We describe an in situ encapsulation approach that allows enzymes to be loaded into silica nanoreactors in well‐defined compositions. The nanoreactors can be combined into integrated systems to produce a desired reaction outcome. We used the selective enzyme co‐compartmentalization and nanoreactor integration to regulate competitive cascade reactions and to modulate the kinetics of sequential reactions involving multiple nanoreactors. Furthermore, we show that the nanoreactors can be efficiently loaded into giant polymer vesicles, resulting in multi‐compartmentalized microreactors.

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

Microbial infections have become a great threat to human health and one of the main risks arises from direct contact with the surfaces contaminated by pathogenic microbes. Herein, a kind of hexagonal column interpenetrated spheres (HCISs) are fabricated by non‐covalent assembly of plant gallic acid with quaternary ammonium surfactants. Different from one‐time burst release of conventional antimicrobial agents, the HCIS acts like a “antimicrobial molecular bank” and releases the antimicrobial ingredients in a multistage way, leading to long‐lasting antimicrobial performance. Taking advantage of strong hydrophobicity and adhesion, HCISs are applicable to various substrates and endowed with anti‐water washing property, thus showing high in vitro antimicrobial efficiency ( 〉 99 %) even after being used for 10 cycles. Meanwhile, HCISs exhibit broad‐spectrum antimicrobial activity against bacteria and fungi, and have good biocompatibility with mammalian cells. Such a low‐cost and portable long‐lasting antimicrobial agent meets the growing anti‐infection demand in public spaces.

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

Chemical reactivity between As and N 2 , leading to the synthesis of crystalline arsenic nitride, is here reported under high pressure and high temperature conditions generated by laser heating in a diamond anvil cell. Single‐crystal synchrotron X‐ray diffraction at different pressures between 30 and 40 GPa provides evidence for the synthesis of a covalent compound of AsN stoichiometry, crystallizing in a cubic P2 1 3 space group, in which each of the two elements is single‐bonded to three atoms of the other and hosts an electron lone pair, in a tetrahedral anisotropic coordination. The identification of characteristic structural motifs highlights the key role played by the directional repulsive interactions between non‐bonding electron lone pairs in the formation of the AsN structure. Additional data indicate the existence of AsN at room temperature from 9.8 up to 50 GPa. Implications concern fundamental aspects of pnictogens chemistry and the synthesis of innovative advanced materials.

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0044-8249, 1521-3757

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

Hydrogen sulfide (H 2 S) is an important endogenous gasotransmitter, but the targeted delivery and real‐time feedback of exogenous H 2 S are still challenging. With the aid of density functional theory (DFT) calculations, we designed a new 1,3‐dithiolium‐4‐olate (DTO) compound, which can react with a strained alkyne via the 1,3‐dipolar cycloaddition and the retro‐Diels–Alder reaction to generate carbonyl sulfide (COS) as the precursor of H 2 S, and a thiophene derivative with turn‐on fluorescence. Moreover, the diphenylamino substituent in DTO greatly increases the mitochondrial targeting of this H 2 S delivery system. Such a bioorthogonal click‐and‐release reaction has integrated three functions in one system for the first time: (1) in situ controllable H 2 S release, (2) concomitant fluorescence response, and (3) mitochondria‐targeted delivery. In addition, we investigated the mitochondrial membrane potential loss alleviation by using this system in H9c2 cells under oxidative stress.

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0044-8249, 1521-3757

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

Nanofluidic ion transport holds high promise in bio‐sensing and energy conversion applications. However, smart nanofluidic devices with high ion flux and modulable ion transport capabilities remain to be realised. Herein, we demonstrate smart nanofluidic devices based on oriented two‐dimensional covalent organic framework (2D COF) membranes with vertically aligned nanochannel arrays that achieved a 2–3 orders of magnitude higher ion flux compared with that of conventional single‐channel nanofluidic devices. The surface‐charge‐governed ion conductance is dominant for electrolyte concentration up to 0.01 M. Moreover, owing to the customisable pH‐responsivity of imine and phenol hydroxyl groups, the COF‐DT membranes attained an actively modulable ion transport with a high pH‐gating on/off ratio of ≈100. The customisable structure and rich chemistry of COF materials will offer a promising platform for manufacturing nanofluidic devices with modifiable ion/molecular transport features.

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0044-8249, 1521-3757

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

While of interest, synthetically feasible access to boryl ligands and complexes remains limited, meaning such complexes remain underexploited in catalysis. For bidentate boryl ligands, oxidative addition of boranes to low‐valent Ir I or Pt 0 are the only examples yet reported. As part of our interest in developing improved group 10 ethylene polymerization catalysts, we present here an optimized synthesis of a novel, rigid borane/phosphine ligand and its Ni 0 σ‐borane complex. From the latter, an unprecedented oxidative dehydrochloroborylation, to give a Ni II boryl complex, was achieved. Furthermore, this new B/P ligand allowed the nickel‐catalyzed polymerization of ethylene, which suggests that Ni 0 σ‐hydroborane complexes act as masked Ni II boryl hydride reagents.

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0044-8249, 1521-3757

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

Polydimethylsiloxane (PDMS), as the benchmark of organophilic membrane materials, still faces challenges for removal of aromatic compounds due to the undesirable transport channels. In this work, we propose to reconstruct the PDMS conformation with tunable side group mobility by introducing phenyl as rigid molecular spacer to relieve steric hindrance of large‐sized aromatic molecules; meanwhile, polymer segments are loosely stacked to provide additional degrees of freedom as increasing the permeant size. Moreover, the reconstructed PDMS is engineered into the composite membrane with prevention of condensation of aromatic compounds in the substrate pores. The resulting thin‐film composite membrane achieved one order of magnitude higher flux (11.8 kg m −2  h −1 ) with an equivalent separation factor (12.3) compared with the state‐of‐the‐art membranes for aromatic removal. The permeant‐customized membrane molecular and microstructure designing strategy opens a new avenue to develop membranes for specific separation targets.

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0044-8249, 1521-3757

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

An energy transfer‐based signal amplification relay concept enabling transmission of bioorthogonally activatable fluorogenicity of blue‐excitable coumarins to yellow/red emitting cyanine frames is presented. Such relay mechanism resulted in improved cyanine fluorogenicities together with increased photostabilities and large apparent Stokes‐shifts allowing lower background fluorescence even in no‐wash bioorthogonal fluorogenic labeling schemes of intracellular structures in live cells. These energy transfer dyads sharing the same donor moiety together with their parent donor molecule allowed three‐color imaging of intracellular targets using one single excitation source with separate emission windows. Sub‐diffraction imaging of intracellular structures using the bioorthogonally activatable FRET dyads by STED microscopy is also presented.

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0044-8249, 1521-3757

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

A series of solid supramolecules based on acrylamide–phenylpyridium copolymers with various substituent groups (P−R: R=−CN, −CO 2 Et, −Me, −CF 3 ) and cucurbit[7]uril (CB[7] ) are constructed to exhibit tunable second‐level (from 0.9 s to 2.2 s) room‐temperature phosphorescence (RTP) in the amorphous state. Compared with other solid supramolecules P−R/CB[7] (R=−CN, −CO 2 Et, −Me), P−CF 3 /CB[7] displays the longest lifetime (2.2 s), which is probably attributed to the fluorophilic interaction of cucurbiturils leading to a uncommon host–guest interaction between 4‐phenylpyridium with −CF 3 and CB[7]. Furthermore, the RTP solid supramolecular assembly (donors) can further react with organic dyes Eosin Y or SR101 (acceptors) to form ternary supramolecular systems featuring ultralong phosphorescence energy transfer (PpET) and visible delayed fluorescence (yellow for EY at 568 nm and red for SR101 at 620 nm). Significantly, the ultralong multicolor PpET supramolecular assembly can be further applied in fields of anti‐counterfeiting and information encryption and painting.

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0044-8249, 1521-3757

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

Herein, we disclose a straightforward, robust, and simple route to access β‐substituted desaturated cyclic amines via an electrochemically driven desaturative β‐functionalization of cyclic amines. This transformation is based on multiple single‐electron oxidation processes using catalytic amounts of ferrocene. The reaction proceeds in the absence of stoichiometric amounts of electrolyte under mild conditions, affording the desired products with high chemo‐ and regioselectivity. The reaction was tolerant of a broad range of substrates and also enables late‐stage β‐C(sp 3 )−H acylation of potentially valuable products. Preliminary mechanistic studies using cyclic voltammetry reveal the key role of ferrocene as a redox mediator in the reaction.

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0044-8249, 1521-3757

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

The targeted synthesis of deep‐ultraviolet (deep‐UV) nonlinear optical (NLO) materials, especially those with non‐π‐conjugated sulfates, has experienced considerable difficulties due to the need to reconcile the oft‐competing requirements for deep‐UV transparency and strong second‐harmonic generation (SHG). We report herein the designed synthesis of the first rare‐earth metal‐based deep‐UV sulfate La(NH 4 )(SO 4 ) 2 by a double‐salt strategy involving introduction of complementary cations, together with optical studies that reveal a short‐wavelength deep‐UV absorption edge (below 190 nm) and the strongest SHG response among deep‐UV NLO sulfates (2.4×KDP). Theoretical calculations and crystal structure analysis suggest that the excellent balance between SHG response and deep‐UV transparency can be attributed to a synergistic interaction of the hetero‐cations La 3+ and [NH 4 ] + , which optimize alignment of the [SO 4 ] tetrahedra and highly polarizable [LaO 8 ] polyhedra.

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

To meet strategic applications, electrochemical reduction of CO 2 into value‐added chemical molecules would be improved by the rational design of advanced electrocatalysts with atomically dispersed active sites. Herein an electrospun‐pyrolysis cooperative strategy is presented to not only modulate the porous structure of the carbon support for favorable charge and mass transfer, but also adjust the bridging structure of atomically dispersed metal species. Typically, the experimental results and theoretical calculations revealed that the unique chemical structure of binuclear nickel bridging with nitrogen and carbon atoms (namely Ni 2 −N 4 −C 2 ) tunes the electronic nature of the d‐states for the optimal adsorption of carbon dioxide and intermediates, thus inducing the substantial enhancement of CO 2 reduction via the thermodynamically more favorable pathway. The identification of such a structure demonstrates the large space to modulate the atomic bridging status for optimizing electrocatalysis.

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

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0044-8249, 1521-3757

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Wiley

2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

Online Resource

0044-8249, 1521-3757

English

Wiley

2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

Online Resource

0044-8249, 1521-3757

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Wiley

2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

This review presents a critical and comprehensive overview of current experimental measurements of complete elastic constant tensors for molecular crystals. For a large fraction of these molecular crystals, detailed comparisons are made with elastic tensors obtained using the corrected small basis set Hartree–Fock method S‐HF‐3c, and these are shown to be competitive with many of those obtained from more sophisticated density functional theory plus dispersion (DFT‐D) approaches. These detailed comparisons between S‐HF‐3c, experimental and DFT‐D computed tensors make use of a novel rotation‐invariant spherical harmonic description of the Young's modulus, and identify outliers among sets of independent experimental results. The result is a curated database of experimental elastic tensors for molecular crystals, which we hope will stimulate more extensive use of elastic tensor information—experimental and computational—in studies aimed at correlating mechanical properties of molecular crystals with their underlying crystal structure.

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

Residue‐selective bioconjugation methods for biomolecules are highly sought to expand the scope of their biological and medical applications. Inspired by the mechanism of the generation of natural vinylogous γ‐pyridones (vPDNs), we have developed a novel unique azaphilone‐based, activation‐free primary‐amine‐selective bioconjugation method for biomolecules. Our strategy allows facile functionalization of primary amine groups in peptides and proteins, including the clinically used therapeutic antibody trastuzumab, by generating a highly stable vPDN linkage. Excellent chemoselectivity toward primary amines also enables the azaphilone derivatives to specifically modify the lipid components of Gram‐positive bacteria while bypassing Gram‐negative bacteria and mammalian cells. The new method shows significant advantages including chemoselectivity, efficiency, flexibility and biocompatibility, and therefore provides a valuable addition to the current toolbox for biomolecule conjugation.

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

The application of reprocessable and reprogrammable soft actuators is limited by the synthetic strategies, 3D‐shaping capabilities, and small deformations. In this work, melt‐processable supramolecular soft actuators based on segmented copolymers containing thiourethane and liquid crystal segments have been prepared via sequential thiol addition reactions in a one‐pot approach using commercially available building blocks. The actuators demonstrated immediate, reversible response and weightlifting capabilities with large deformations up to 32 %. Through exploiting the supramolecular cross‐links, the material could be recycled and reprogrammed into 3D actuators and welded into an actuator assembly with different deformation modes. Our work offers a one‐pot synthesis and straightforward melt‐processable approach to prepare supramolecular soft actuators with large deformations that can be reprocessed and reprogrammed into arbitrary 3D shapes.

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2022

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

We describe a titanocene(III)‐catalyzed deuterosilylation of epoxides that provides β‐deuterated anti‐Markovnikov alcohols with excellent D‐incorporation, in high yield, and often excellent diastereoselectivity after desilylation. The key to the success of the reaction is a novel activation method of Cp 2 TiCl 2 and ( t BuC 5 H 4 ) 2 TiCl 2 with BnMgBr and PhSiD 3 to provide [(RC 5 H 4 ) 2 Ti(III)D] without isotope scrambling. It was developed after discovering an off‐cycle scrambling with the previously described method. Our precision deuteration can be applied to the synthesis of drug precursors and highlights the power of combining radical chemistry with organometallic catalysis.

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Angewandte Chemie, Wiley, Vol. 134, No. 6 ( 2022-02)

Under topological guidance, the self‐assembly process based on a tetratopic porphyrin synthon results in a hydrogen‐bonded organic framework (HOF) with the predicted square layers topology ( sql ) but unsatisfied stability. Strikingly, simply introducing a transition metal in the porphyrin center does not change the network topology but drastically causes noticeable change on noncovalent interaction, orbital overlap, and molecular geometry, therefore ultimately giving rise to a series of metalloporphyrinic HOFs with high surface area, and excellent stability (intact after being soaked in boiling water, concentrated HCl, and heated to 270 °C). On integrating both photosensitizers and catalytic sites into robust backbones, this series of HOFs can effectively catalyze the photoreduction of CO 2 to CO, and their catalytic performances greatly depend on the chelated metal species in the porphyrin centers. This work enriches the library of stable functional HOFs and expands their applications in photocatalytic CO 2 reduction.

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2022

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