Two‐dimensional (2D) mesoporous heterostructures combining ultrathin nanosheet morphology, periodic porous surface structures and diverse hybrid compositions have recently emerged and become increasingly important for renewable energy storage and electronics. However, it remains a great challenge to develop a universal method to prepare 2D mesoporous heterostructures. Here, we report a composite micelle‐directed interfacial assembly method to synthesize vertical heterostructures with ultrathin 2D...
Sat Jul 11, 2020 22:15
An enantioselective bifunctional squaramide‐catalyzed detrifluoroacetylative alkylation reaction under electrochemical conditions has been developed. The unified strategy based on this key tandem methodology has been divergently explored for the asymmetric synthesis of fluorine‐containing target molecules with good stereocontrol (up to 95% ee ). Furthermore, this catalytic asymmetric detrifluoroacetylative alkylation reaction demonstrated the benefits of combining electrosynthesis and organocatalysis...
Sat Jul 11, 2020 22:06
Dealkenylative alkenylation of alkene C(sp3)‐C(sp2) bonds has been an unexplored area for C‐C bond formation. Herein, we report 64 examples of β‐alkylated styrene derivatives synthesized through the reactions of readily accessible feedstock olefins with β‐nitrostyrenes through ozone/Fe(II)‐mediated radical substitution. These reactions proceed with good efficiency and high stereoselectivity under mild conditions and tolerate an array of functional groups. We demonstrate the applicability of the strategy...
Sat Jul 11, 2020 22:04
In the scientific race to build up photoactive electron donor‐acceptor systems with increasing efficiencies, little is known about the interplay of their building blocks when integrated into supramolecular nanoscale arrays, particularly in aqueous environments. Here, we describe an aqueous donor‐acceptor ensemble whose emergence as a nanoscale material renders it remarkably stable and efficient. We have focused on a tetracationic zinc phthalocyanine (ZnPc) featuring pyrenes, which shows an unprecedented...
Sat Jul 11, 2020 22:00
To activate electronic and optical functions of the redox‐active metal‐organic framework, (Me 2 NH 2 )[In III (TTFTB)]·0.7C 2 H 5 OH· DMF (Me 2 NH 2 @ 1, TTFTB = tetrathiafulvalene‐tetrabenzoate, DMF = N,N ‐dimethylformamide), has been exchanged by tetrathiafulvalenium (TTF •+ ) and N,N ' ‐dimethyl‐ 4,4 ' ‐bipyridinium (MV 2+ ). These cations provide electron carriers and photosensitivity. The exchange retains the crystallinity allowing single‐crystal to single‐crystal...
Sat Jul 11, 2020 21:45
We report a new mass spectrometric method for detecting electrogenerated intermediates. This approach is based on simultaneous activation of electrospray ionization and redox reaction on a wireless bipolar ultramicroelectrode, which is fabricated in the tip of a quartz nanopipette. The hollow structure of the ultramicroelectrode permits rapid transferring the transient species from electrode‐electrolyte interfaces into gas phase for mass spectrometric identification on the time scale of microseconds....
Sat Jul 11, 2020 21:41
Spatial organization of electron donor‐acceptor (D‐A) supramolecular assembly is critical to the photophysical processes involved in solar energy conversion systems. Subtle variation in geometry, i.e. D‐A distance and transition dipole arrangement can influence kinetics and thermodynamics of the electron transfer (ET) process. To acquire an insight into the structure‐function correlation, making of modular, crystalline materials is advantageous. In this regard, we demonstrate a redox‐active, crystalline...
Sat Jul 11, 2020 11:16
Replacing the Pb–X octahedral building unit of A I PbX 3 perovskites (X = halide) with a pair of edge‐sharing Pb–X octahedra affords the expanded perovskite analogs: A II Pb 2 X 6 . We report eight members of this new family of materials. In 3D hybrid perovskites, orbitals from the organic molecules do not participate in the band edges. In contrast, the more spacious inorganic sublattice of the expanded analogs accommodates larger pyrizinium‐based cations with low‐lying π* orbitals that...
Fri Jul 10, 2020 22:14
You got the silver : An ultrastable, small {Ag7}5+ nanocluster was synthesized within an unprecedented triangular hollow polyoxometalate (POM) framework [Si3W27O96]18−. The cluster showed unique {Ag7}5+‐to‐POM charge transfer bands in both visible‐ and UV‐light regions. Abstract Small Ag n nanoclusters (n <10) have been emerging as promising materials as sensing, biolabeling, and catalysis because of their unique electronic states and optical properties. However, studying synthesis,...
Fri Jul 10, 2020 22:00
Aluminium batteries constitute a safe and sustainable high–energy‐density electrochemical energy‐storage solution. Viable Al‐ion batteries require suitable electrode materials that can readily intercalate high‐charge Al 3+ ions. Here, we investigate the Al 3+ intercalation chemistry of anatase TiO 2 and how chemical modifications influence the accommodation of Al 3+ ions. We use fluoride‐ and hydroxide‐doping to generate high concentrations of titanium vacancies. The coexistence of these...
Fri Jul 10, 2020 21:14
Non‐centrosymmetric polar compounds have important technological properties. Reported perovskite oxynitrides show centrosymmetric structures and for some of them high permittivities have been observed, ascribed to local dipoles induced by partial order of nitride and oxide. Here we report the first hexagonal perovskite oxynitride BaWON2, that shows a polar 6H polytype. Synchrotron X‐ray and neutron powder diffraction, and annular bright‐field in scanning transmission electron microscopy indicate...
Fri Jul 10, 2020 20:44
Gastrin‐releasing peptide receptor (GRPr) plays proliferative and inflammatory roles in living systems. Here, we report a highly selective GRPr antagonist (JMV594)‐tethered iridium(III) complex for probing GRPr in living cancer cells and immune cells. This probe not only exhibited desirable photophysical properties, but also displayed negligible cytotoxicity, overcoming the inherent toxicity of the iridium(III) complex. In particular, its long emission lifetime enabled its luminescence signal to...
Fri Jul 10, 2020 20:44
A conceptually novel approach is described for the synthesis of six‐membered cyclic carbonates derived from carbon dioxide. The approach utilizes homoallylic precursors that are converted into five‐membered cyclic carbonates having a beta‐positioned alcohol group in one of the ring substituents. The activation of the pendent alcohol group through an N ‐heterocyclic base allows for equilibration towards a thermodynamically disfavored six‐membered carbonate analogue that can be conveniently trapped...
Fri Jul 10, 2020 19:15
While the art of DNA origami has been investigated extensively in recent years and demonstrated to work in a reliable manner, precise engineering of such patterns with polymers represents an emerging topic. Compared to conventional top‐down approaches ( i.e. lithography) or bottom‐up functionalization techniques ( i.e. self‐assembly), the combination of DNA origami nanostructures and polymers provides a new toolbox to access defined structures in the 100 nm range. In general, DNA origami...
Fri Jul 10, 2020 16:44
Multi‐component MOFs contain multiple sets of unique and hierarchical pores, with different functions for different applications, distributed in their inter‐linked domains. Herein, we report the construction of a class of precisely aligned flexible‐on‐rigid hybrid‐phase MOFs with unique rods‐on‐octahedron morphology. We demonstrated that hybrid‐phase MOFs can be constructed based on two prerequisites: the partially matched topology at the interface of the two frameworks, and the structural flexibility...
Fri Jul 10, 2020 15:14
Porosity and acidity are influential properties in the rational design of solid‐acid catalysts. Probing the physicochemical characteristics of an acidic zeotype framework at the molecular level can provide valuable insights in understanding intrinsic reaction pathways, for affording structure‐activity relationships. Herein, we employ a variety of probe‐based techniques (including positron annihilation lifetime spectroscopy (PALS), FTIR and solid‐state NMR) to demonstrate how a hierarchical design...
Fri Jul 10, 2020 13:14
The reaction of hexachlorophosphazene, P3N3Cl6, with SO3 leads to the new sulfur nitride‐oxide S6N2O15. The compound displays an extraordinarily low nitrogen content and exhibits a bicyclic cage structure according to the formulation N{S(O)2O(O)2S}3N, with both nitrogen atoms in trigonal planar coordination of sulfur atoms. Interestingly, the new nitride‐oxide can be also seen as the anhydride of nitrido‐tris‐sulfuric acid, N(SO3H)3.
Fri Jul 10, 2020 11:49
Emissive silver nanoclusters formed with cytosine‐loop hairpin DNA sequences self‐assemble as highly emissive dimers exhibiting a head‐to‐head interaction interface. These dimeric species only form emissive dimers when synthesis is initiated from DNA in the monomeric hairpin conformation. The orange emissive AgNCs were found to be composed of 12 Ag per dimer with the dimerization mediated by the nanocluster. Abstract Fluorescent, DNA‐stabilized silver nanoclusters (DNA‐AgNCs) are applied...
Fri Jul 10, 2020 11:42
Go with the glow : A two‐step process has been developed that transforms parent diketopyrrolopyrrole into structures with up to 10 fused rings. The absorptions are bathochromically shifted to the deep‐red region and strong red emission is seen, even in nonpolar solvents, despite the presence of NO2 groups. Abstract Red‐emissive π‐expanded diketopyrrolopyrroles (DPPs) with fluorescence reaching λ=750 nm can be easily synthesized by a three‐step strategy involving the preparation of diketopyrrolopyrrole...
Fri Jul 10, 2020 11:40
A class of chiral naphthyridine diimine ligands (NDI* ) is described. The application potential of these ligands for asymmetric catalysis is illustrated by a reductive enantioselective bi‐nuclear nickel‐catalyzed alkylidene transfer of 1,1‐dichloroalkenes to olefins, yielding synthetically valuable alkylidenecyclopropanes in high yields and enantioselectivities. Abstract A novel class of chiral naphthyridine diimine ligands (NDI*) readily accessible from C2 ‐symmetric 2,6‐di‐(1‐arylethyl)anilines...
Fri Jul 10, 2020 11:38
Collective thinking : Concise collective total syntheses of cyclopiane‐type diterpenes (−)‐conidiogenone B, (−)‐conidiogenone, and (−)‐conidiogenol were accomplished in 14–17 steps. The approach features a HAT‐mediated alkene–nitrile cyclization, a Nicholas/Pauson–Khand reaction, and a Danheiser annulation to afford the congested angular triquinane skeleton. Abstract Cyclopianes are novel diterpenes featuring a highly strained 6/5/5/5 tetracyclic core embedded with 6–8 consecutive stereocenters....
Fri Jul 10, 2020 11:38
The activation of a gold‐chloride complex by halogen‐bonding‐based Lewis acids is described as the first case of metal‐ligand bond cleavage by inert halogen bond donors. Iodine(I) and iodine(III) derivatives provided excellent performance in two proof‐of‐principle reactions. Comparative experiments for both activators strongly suggest halogen bonding as the mode of activation. Abstract In recent years, the non‐covalent interaction of halogen bonding (XB) has found increasing application...
Fri Jul 10, 2020 11:38
Two step, one step : A mixed‐valence FeIII/FeII complex 1 was synthesized using [(Tp4‐Me)FeIII(CN)3]− to link with a FeII‐triazole moiety. Complex 1 underwent a metal‐to‐metal charge transfer (MMCT) between FeIII and one of the FeII sites after heat treatment, resulting a new isostructural phase of 1 a . The MMCT can turn the two‐step spin crossover (SCO) behavior of 1 into one‐step SCO behavior of 1 a . Abstract It is promising and challenging to manipulate the electronic structures...
Fri Jul 10, 2020 11:37
Unforeseen performance : The study of the chemical and morphological transformation of intermetallic Al2Pt, a precursor of a new composite material, under the harsh oxidative conditions of the oxygen evolution reaction (OER) is accompanied by its electrochemical characterization at different stages of long‐term operation. Abstract The production of hydrogen via water electrolysis is feasible only if effective and stable catalysts for the oxygen evolution reaction (OER) are available. Intermetallic...
Fri Jul 10, 2020 11:37
In the blink of an I : An unprecedented metal‐free C(sp3)−H fluorination using nucleophilic fluoride as a fluorine source is reported. The inherent performance of amidyl radicals in the context of halogen catalysis allows perfect control of position selectivity for the synthesis of tert‐alkyl fluorides. With this method, direct access to 1,3‐ and 1,4‐aminofluorines can be achieved with homogeneous experimental conditions. Abstract Iodine catalysis was developed for aliphatic fluorination...
Fri Jul 10, 2020 11:36
Catalysis with a twist : Transition‐metal nitride single crystals are grown on the 2 cm scale to create well‐defined structures at twisted surfaces. High catalytic activity and stability toward non‐oxidative dehydrogenation of ethane to ethylene is observed. Abstract Porous single crystals which combine ordered lattice structures and disordered inter‐connected pores would provide an alternative to create twisted surface in porous microstructures. Now, transition‐metal nitride Nb4N5 and...
Fri Jul 10, 2020 11:35
Well‐dispersed Ru nanoparticles with narrow size distribution form on a metal–organic framework to afford a catalyst that displays excellent performance in the indirect and sustainable methanation of CO2 using amino alcohols as effective relay molecules. Abstract Methanation of carbon dioxide (CO2) is attractive within the context of a renewable energy refinery. Herein, we report an indirect methanation method that harnesses amino alcohols as relay molecules in combination with a catalyst...
Fri Jul 10, 2020 11:34
Ti silicates, and in particular Titanium Silicalite‐1 (TS‐1), are nowadays important catalysts for several partial oxidation reactions in the presence of aqueous H 2 O 2 as oxidant. Despite the numerous studies dealing with this material, some fundamental aspects are still unfathomed. In particular, the structure and the catalytic role of defective Ti sites, other than perfect tetrahedral sites recognized as main active species, has not been quantitatively discussed in the literature. In this...
Fri Jul 10, 2020 11:44
A new family of phosphine‐ligated dicyanoarylgold(III) complexes has been prepared and their reactivity towards reductive elimination has been studied in detail. Both, a highly positive entropy of activation and a primary 12/13 C KIE suggest a late concerted transition state while Hammett analysis and DFT calculations indicate that the process is asynchronous. As a result, a distinct mechanism involving an asynchronous concerted reductive elimination for the overall C(sp 2 )‐C(sp)N bond forming...
Fri Jul 10, 2020 11:44
Virus and virus‐like particles (VLPs) are very attractive biological subjects for self‐assembly manipulation and templated synthesis of nanomaterials. However, the fundamental studies and applications are often constrained by problems associated with their structural weakness. Here we present a strategy of interfacially bridging covalent network within tobacco mosaic virus (TMV) VLPs to bring outstanding structural properties and functionalities. We arranged T103C cysteine to laterally conjugate...
Thu Jul 09, 2020 22:52
The direct, nonoxidative conversion of methane on silica‐confined single‐atom iron catalyst (Fe 1 ©SiO 2 ) by Bao et al . ( Science , 2014, 344 , 616) is a landmark discovery in catalysis science. However, the initially proposed gas‐phase reaction mechanism has been much debated. Here, we report a surface reaction mechanism by comprehensive computational modelling and simulations. It is demonstrated that the activation of methane occurs at the single iron site, whereas the dissociated methyl...
Thu Jul 09, 2020 22:51
Two‐dimensional (2D) materials host great potential for environmental gaseous molecules detection in the age of emerging Internet of things owing to their fascinating electronic properties, large surface‐to‐volume ratio and feasibility to high integration. However, it remains a challenge to develop trace oxygen sensing 2D materials and devices with low detection limit at sub‐ppm range. Here, we exploit a high‐preforming resistive‐type trace oxygen sensor based on 2D high‐mobility semiconducting Bi...
Thu Jul 09, 2020 22:50
Spin‐dependent conduction and polarization in chiral polymers were studied for polymers organized as self‐assembled monolayers with conduction along the polymer backbone, namely, along its longer axis. Large spin polarization and magnetoresistance effects were observed, showing a clear dependence on the secondary structure of the polymer. The results indicate that the spin polarization process does not include spin flipping and thus results from backscattering probabilities for the two spin states....
Thu Jul 09, 2020 22:00
In soft matter, thermal energy causes molecules to continuously translate and rotate, even in crowded environments, thereby impacting the spatial organization and function of most molecular assemblies, such as lipid membranes. Directly measuring the orientation and spatial organization of large collections (>3000 molecules/µm 2 ) of single molecules with nanoscale resolution remains elusive. In this paper, we utilize SMOLM, single‐molecule orientation localization microscopy, to directly measure...
Thu Jul 09, 2020 20:49
Lead‐free halide perovskite of A 3 Sb 2 Br 9 is utilized as photocatalyst for the first time to C (sp 3 )‐H bonds activation. A 3 Sb 2 Br 9 nanoparticles (A 3 Sb 2 Br 9 NPs) with different ratios of Cs and MA show different photocatalytic activity for toluene oxidation and the photocatalytic performance is enhanced when increasing the amount of Cs. We reveal that the octahedron distortion caused by A‐site cations can change the electronic property of X‐site ions and further...
Thu Jul 09, 2020 20:30
Lantibiotics are a type of ribosomally synthesized and post‐translationally modified peptides (termed lanthipeptides) with often potent antimicrobial activity. Herein, we report the discovery of a new lantibiotic, lexapeptide, using the Library EXpression Analysis System (LEXAS) approach. Lexapeptide has rare structural modifications, including N‐terminal (N,N)‐dimethyl phenylalanine, C‐terminal (2‐aminovinyl)‐3‐methyl‐cysteine, and D‐Ala. The characteristic lanthionine moiety in lexapeptide is formed...
Thu Jul 09, 2020 19:19
Electrolyte modulation has been reported to simultaneously suppress polysulfide shuttle effect and lithium dendrite formation of lithium‐sulfur (Li‐S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been intensively ignored, which dramatically limits the cycle life and energy density of practical Li‐S pouch cells. Herein, we demonstrate that a rational combination of selenium doping, core‐shell hollow host structure, and fluorinated...
Thu Jul 09, 2020 19:14
Mesoporous core‐shell nanostructures holding controllable ultra‐large open channels in their nanoshells are of great interests for the development of new catalytic platforms, electrochemical energy systems, and biological macromolecular carriers. However, soft template‐directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored...
Thu Jul 09, 2020 18:19
O‐Sulfation is an important chemical code widely existing in bioactive molecules, but the scalable and facile synthesis of complex bioactive molecules carrying O‐sulfation remains challenging. Herein, we report a general approach to O‐sulfation via the Sulfur (VI) Fluoride Exchange (SuFEx) reaction between aryl fluorosulfates and silylated hydroxyl groups. Efficient sulfate diester formation was achieved through systematic optimization of the electronic properties of aryl fluorosulfates. The versatility...
Thu Jul 09, 2020 17:52
Growth of covalent organic frameworks (COFs) as single crystals is extremely challenging. Inaccessibility of open‐structured single‐crystal COFs prevents the exploration of structure‐oriented applications. Herein we report for the first time a non‐interpenetrated single‐crystal COF, LZU‐306, which possesses the open structure constructed exclusively via covalent assembly. With a high void volume of 80%, LZU‐306 was applied to investigate the intrinsic dynamics of reticulated tetraphenylethylene...
Thu Jul 09, 2020 17:52
A novel separation–sensing membrane performing precise real‐time serum analysis during blood drawing
Dynamic and on‐site analysis of serum from human blood is crucial particularly for making decisions during clinical surgery and emergency treatments. However, state‐of‐the‐art blood assay methods can only collect single or discrete data of physiological analytes, remaining great challenge in online report of dynamic fluctuation of key analytes. Here we propose a novel separation–sensing membrane by constructing a heterogeneous‐nanostructured architecture in which a surface nanoporous layer continuously...
Thu Jul 09, 2020 17:49
Herein, we introduce the cyclic 8π‐electron (C8π) molecule N , N ′‐diaryl‐dihydrodibenzo[ a , c ]phenazines ( DPAC ) as a dual‐functional donor to establish a series of new donor‐linker‐acceptor (D‐L‐A) dyads DLA1 ~ DLA5 . The excited‐state bent‐to‐planar dynamics of DPAC regulate the donor’s energy gap, while the acceptors A1 ~ A5 are endowed with different energy gaps and HOMO/LUMO levels. As a result, the rate and efficiency of the excited‐state electron transfer versus energy...
Thu Jul 09, 2020 16:52
Efficient electron communication between molecular catalyst and support is critical for heterogeneous molecular electrocatalysis and yet it is often overlooked during the catalyst design. Taking CO 2 electro‐reduction on tetraphenylporphyrin cobalt (PCo) immobilized onto graphene as an example, we demonstrate that adding a relay molecule improves the interfacial electron communication. While the directly immobilized PCo on graphene exhibits relatively poor electron communications, it is found that...
Thu Jul 09, 2020 16:51
(Oxo)Nitridophosphates have recently been identified as a promising compound class for application in the field of solid‐state lighting. Especially, the latest medium‐pressure syntheses under ammonothermal conditions draw attention of the semi‐conductor and lighting industry on nitridophosphates. In this contribution, we introduce hot isostatic presses as a new type of medium‐pressure synthetic tool, further simplifying nitridophosphate synthesis. In a second step, phosphorus nitride was replaced...
Thu Jul 09, 2020 16:47
It turns blue ! The first crystalline three‐dimensional bimetallic halide of [(NH4)2]CuPbBr5 exhibits strong narrow blue emission with high PLQY of 32 % as well as remarkable structural and optical stabilities. This structural design strategy is entirely different from the modification methods over CsPbX3 quantum dots and paves a unique way to realize blue light emission based on single‐crystalline hybrid metal halides. Abstract Considering the instability and low photoluminescence quantum...
Thu Jul 09, 2020 13:01
Radical rotations about Si–P bonds : Muonium, a light isotope of H, reacts with phosphasilenes to form P‐centred and/or Si‐centred radicals. In some cases, multiple rotamer conformations of the same radical can be detected, depending on the nature of the substituents on the parent phosphasilene. Abstract Understanding the characteristics of radicals formed from silicon‐containing heavy analogues of alkenes is of great importance for their application in radical polymerization. Steric and...
Thu Jul 09, 2020 13:01
The accelerator and brake of a nanozyme are enabled by mimicking molecular structure of enzymes. Owing to the heme‐like Fe‐N x molecular structure and variable interactions with different substrates, Fe‐N‐C nanozyme not only accelerates P450‐like drug metabolization reactions but also demonstrates inhibition behaviors with mechanism similar to P450 upon co‐existence of other food and drugs. Abstract Emerging as a cost‐effective and robust enzyme mimic, nanozymes have drawn increasing...
Thu Jul 09, 2020 12:52
Crystalline red phosphorus (cRP) with a layered structure are synthesized on a large scale by an efficient chemical vapor transport method and few‐layer 2D nanoribbons are exfoliated. Theoretical and experimental studies demonstrate that the cRP nanoribbons are promising in electrochemical nitrogen reduction in aqueous solutions under ambient conditions. Abstract Two dimensional (2D) nanoribbons constitute an emerging nanoarchitecture for advanced microelectronics and energy conversion...
Thu Jul 09, 2020 12:49
Make a difference together : Heteroatoms were inserted into spiro‐conjugated triangulenes and the resultant structure–property relationships were explored. At the focus are the molecular and electronic structure of these compounds, their dual fluorescence (core and wings), and their aggregation behavior in solvent/antisolvent mixtures. Abstract We report on the impact of the central heteroatom on structural, electronic, and spectroscopic properties of a series of spirofluorene‐bridged heterotriangulenes...
Thu Jul 09, 2020 12:49
The iodination of cyclo ‐E5 complexes was introduced for the synthesis of polypnictogen complexes. In the reaction of [Cp*M(η5‐P5)] (M=Fe, Ru) with iodine, [Cp*MP6I6]+ cations with tripodal cyclo‐{P(PI2)}3 ligands were formed. With cyclo‐As5 complexes, the first di‐cationic Fe‐As triple decker, the first monocationic Ru‐As5 triple decker and two isomers of a complex with a unique tetramer of iodoarsinidene units were obtained. Abstract In a high‐yield one‐pot synthesis,...
Thu Jul 09, 2020 12:48
An efficient photoelectrochemical dehydrogenative cross‐coupling of heteroarenes with C(sp3)−H species is described. Chlorine atoms, which are produced by light irradiation of anodically generated Cl2 from Cl−, abstract a hydrogen atom from C(sp3)−H bonds to afford carbon radicals. The latter undergo Minisci alkylation to afford the final functionalized heteroarene products. Abstract Heteroarenes are structural motifs found in many bioactive compounds and functional materials. Dehydrogenative...
Thu Jul 09, 2020 12:48
Protein heterocatenanes could be readily and modularly synthesized in cellulo using a programmed sequence of post‐translational processing events, including intramolecular chain entanglement, in situ backbone cleavage, and spontaneous cyclization. The catenane topology of the designed protein was rigorously proven by X‐ray crystallography. Abstract Herein, we report the biosynthesis of protein heterocatenanes using a programmed sequence of multiple post‐translational processing events...
Thu Jul 09, 2020 12:47
Polyimide was employed as a low‐cost and high‐capacity solid material to boost the capacity of pH‐neutral 2,7‐AQDS electrolyte to 97 Ah L−1. Through in situ FTIR spectroscopic study, a hydrogen‐bonding mediated reaction mechanism was disclosed. Abstract Aqueous organic redox flow batteries (AORFBs) have received considerable attention for large‐scale energy storage. Quinone derivatives, such as 9,10‐anthraquinone‐2,7‐disulphonic acid (2,7‐AQDS), have been explored intensively owing to...
Thu Jul 09, 2020 12:46
Rotational spectra of tetrahydro‐2‐furoic acid dimers reveal that simple considerations of thermodynamic or kinetic control are insufficient to rationalize the abundances of the observed dimers. Instead, understanding the energetic interconnectivity of the dimeric network driven in part by chirality is required to unravel the mysteries. A novel chiral self‐tag approach for ee determination is tested. Abstract Chirality recognition in dimers of tetrahydro‐2‐furoic acid (THFA) was studied...
Thu Jul 09, 2020 12:45
Flow with it : Dehydrative amination of phenols under continuous‐flow conditions has been developed. In an integrated packed‐bed flow system containing heterogeneous Pd catalysts, phenols reacted with amines to obtain aryl amines and small amounts of easily removable co‐products. The method has high product selectivity and excellent functional‐group tolerance, so that variously substituted aryl amines can be selectively prepared in high yields. Abstract Aryl amines are important pharmaceutical...
Thu Jul 09, 2020 12:43
A high sodium content (0.85) and plateau‐free P2‐type cathode, Na0.85Li0.12Ni0.22Mn0.66O2, is developed for sodium‐ion batteries. The sodium content promises a large specific capacity of 123.4 mA h g−1 with an average working voltage as high as 3.5 V. The complete solid‐solution reaction over a wide voltage range ensures small volume variation (1.7 %) and fast Na+ kinetics (10−10 to 10−11 cm2 s−1), contributing to both excellent cycling stability and rate capability. Abstract P2‐type layered...
Thu Jul 09, 2020 12:43
Self‐folding DNA ribbon : A programmable DNA ribbon is constructed from long‐chain DNA molecules with a user‐defined repetitive padlock sequence. The DNA ribbon can be further combined with gold nanoparticles (AuNPs) to create a composite nanomaterial that contains an AuNP core and a high‐density DNA crown carrying a cancer‐cell‐targeting DNA aptamer, a fluorescent tag for location tracking, and a cell‐killing drug. Abstract Herein, we report on the design of a programmable DNA ribbon using...
Thu Jul 09, 2020 12:42
The sweet spot : Quantification of protein N‐glycosylation variants by mass spectrometry is biased in the presence of glycation, a modification often observed in biopharmaceuticals. A novel computational method is able to eliminate this bias. Abstract N‐glycosylation may affect the safety and efficacy of biopharmaceuticals and is thus monitored during manufacturing. Mass spectrometry of the intact protein is increasingly used to reveal co‐existing glycosylation variants. However, quantification...
Thu Jul 09, 2020 12:42
Mutant‐selective allosteric EGFR degraders (blue) mediate the formation of the cereblon (CRBN)–degrader–EGFR ternary complex, resulting in mutant EGFR, but not WT, degradation. The lead degrader, DDC‐01‐163 is broadly effective against drug‐resistant mutants, and exhibits enhanced potency when combined with an inhibitor, osimertinib. The targeted EGFR degradation represents a promising strategy to overcome drug resistance. Abstract Targeting epidermal growth factor receptor (EGFR) through...
Thu Jul 09, 2020 12:42
Transient self‐assembly of DNA‐based nanostructures is achieved by purely synthetic chemical reactions. Inspired by the redox signalling employed by cells, we redox cycles of disulfide‐bond formation/breakage are employed to kinetically control the assembly and disassembly of tubular DNA nanostructures in a highly controllable and reversible fashion. Abstract Synthetic DNA has emerged as a powerful self‐assembled material for the engineering of nanoscale supramolecular devices and materials....
Thu Jul 09, 2020 12:41
meta ‐Selective C−H arylation : An activated norbornene traps the ortho‐palladation intermediate in the ortho‐C−H metalation of fluoroarenes and is then relayed to the meta position, leading to meta‐selective C−H arylation. A dual‐ligand system is crucial for the observed high reactivity and selectivity. Applying this approach to simple benzene or other arenes also affords arylation products with good yields and site selectivity. Abstract Fluorine is known to promote ortho‐C−H...
Thu Jul 09, 2020 12:38
The Mechanism of the Magnetodielectric Response in a Molecule‐Based Trinuclear Iron Cluster Material
Cluster compound : The mechanism of the magnetodielectric response in a trinuclear iron cluster, [Fe3O(CH3COO)6(py)3](py), was investigated. It is shown that the magnetodielectric response is induced by spin‐ and charge‐frustration of the trinuclear iron cluster. Abstract Magnetodielectric response mechanisms are critical for the rational design and synthesis of molecule‐based magnetodielectric materials. Herein, the magnetodielectric response was investigated in the molecule‐based material...
Thu Jul 09, 2020 12:38
Squeezing electrons by milling : Macroscopic mechanical forces transduced by ball milling are capable of inducing electrical polarization in piezoelectric BaTiO3. The electropotential of the strained piezoelectric material was harvested to trigger the reduction of a CuII complex into an active CuI catalyst for mechanochemical solvent‐free ATRC reactions. Abstract The formation and regeneration of active CuI species is a fundamental mechanistic step in copper‐catalyzed atom transfer radical...
Thu Jul 09, 2020 12:37
As an emerging member of the graphene family, structurally defined graphene nanoribbons (GNRs) have shown promising applications in various fields. The evaluation of the degradability of GNRs is particularly important for assessing the persistence level and risk of these materials in living organisms and the environment. However, there is a void in the study of the degradation of GNRs. Here, we report the degradation behavior of GNRs in the presence of human myeloperoxidase (hMPO) or treated with...
Thu Jul 09, 2020 12:24
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