An anthracene–naphthalenediimide donor–acceptor pair is assembled in a well‐defined geometry, as a linker in a crystalline porous metal–organic framework (MOF). In response to the guest encapsulation/removal, the dynamic paddle‐wheel node of the MOF undergoes reversible deformation and subsequently exhibits reversible electron transfer within the donor–acceptor pair. Abstract We demonstrate a redox‐active, crystalline donor–acceptor (D‐A) assembly in which the electron transfer (ET) process...
Tue Sep 01, 2020 12:06
Hop as far as possible: Long‐range energy migration in DNA cause damages 105 Å away from the site of light absorption. The evidence of long‐range formation of cyclobutane pyrimidine dimers is fundamental for our understanding of DNA photodamaging. Abstract A new DNA architecture addresses the question, how far energy migrates in DNA and forms cyclobutane pyrimidine dimers (CPDs) as photodamages causing skin cancer. The 3‐methoxyxanthone nucleoside allows site‐selective photoenergy injection...
Tue Sep 01, 2020 12:05
This article communicates a series of highly active organoboron catalysts for coupling of CO2 and epoxides with merits of scalable preparation, thermostability, and recyclability. The metal‐free catalysts show high reactivity towards a wide scope of cyclic carbonates (14 examples) and can withstand a high temperature up to 150 oC. Compared with most of the current metal‐free catalytic systems involved using mol% catalyst loading, the catalytic capacity of our catalyst can be enhanced by three orders...
Tue Sep 01, 2020 11:33
Solid‐state transformations in metal‐organic framework (MOF) systems are important phenomena and have led to the creation of new MOF structures. Solid‐state transformations from interpenetrated to non‐interpenetrated networks involving rearrangement of secondary building units (SBUs) in a single‐crystal‐to‐single‐crystal (SCSC) fashion have not been explored to date. Herein, we report the sequential, thermally stimulated solid‐state transformations in a barium‐organic framework ( UPC‐600 ). The...
Tue Sep 01, 2020 11:33
Charge‐transfer based surface‐enhanced Raman scattering (SERS) is a promising tool for chiral‐label‐free discrimination of small aromatic molecules with the advantage of synchronous distinction and identification. As discussed by Y. Wang, Z. Yu, Y. Ozaki et al. in their Research Article (DOI: https://doi.org/10.1002/anie.20200777110.1002/anie.202007771), a versatile SERS chiral discrimination sensor has demonstrated excellent performance and successful recognition of more than 10 kinds of chiral...
Mon Aug 31, 2020 22:00
Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β ‐CaGe 2 layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new...
Mon Aug 31, 2020 21:48
The synthetically versatile pinacol boronic ester group (Bpin) is generally thought of as a bulky moiety due to the two adjacent quaternary sp 3 ‐hydribized carbon atoms in its diol backbone. However, recent diastereoselective reactions reported in the literature have cast doubt on this perception. Herein, we report a detailed experimental and computational analysis of Bpin and structurally related boronic esters which allows us to determine three different steric parameters for the Bpin group:...
Mon Aug 31, 2020 20:51
Matrix effects can compromise ionization and hence reliability of electrospray ionisation mass spectrometry (ESI‐MS), making sample clean‐up including protein removal critical in bioanalysis. Automation of protein removal protocols is challenging. Here, an electrokinetic extraction (EkE) syringe is presented allowing for on‐line electrokinetic removal of serum proteins before ESI‐MS. The method relies on the electrophoretic migration of charged serum proteins away from neutral target analytes in...
Mon Aug 31, 2020 20:26
Fused‐ring electron acceptors have made significant progress in recent years, while the development of fully non‐fused ring acceptors has been unsatisfactory. Here, two fully non‐fused ring acceptors, o ‐4TBC‐2F and m ‐4TBC‐2F , were designed and synthesized. By regulating the location of the hexyloxy chains, o ‐4TBC‐2F formed planar backbones, while m ‐4TBC‐2F displayed a twisted backbone. Additionally, the o ‐4TBC‐2F film showed a markedly red‐shifted absorption after thermal annealing,...
Mon Aug 31, 2020 20:22
Inspired by the amino acid composition of natural protein surfaces, we developed a zwitterionic cloak containing multi‐layers of short alternating glutamic acid and lysine (EK) peptides as a facile, highly effective and low‐immunogenicity approach for the protection and delivery of biotherapeutics. Each EK layer grafted to proteins provides multiple times of new lysine reaction sites for the growth of subsequent EK layers. This unique design allows EK peptides to achieve high coating density on proteins,...
Mon Aug 31, 2020 20:20
Chemical bonds are traditionally assigned as electron‐sharing or donor‐acceptor/dative. External criteria such as the nature of the dissociation process, energy partitioning schemes or quantum chemical topology are invoked to assess the bonding situation. However, for systems with marked multi‐reference character, this binary categorization might not be precise enough to render the bonding properties. A third scenario can be foreseen: spin polarized bonds . To illustrate this, we present the case...
Mon Aug 31, 2020 20:20
Developing new principles and techniques with high neuronal compatibility for quantitatively monitoring dynamics of neurochemicals is essential for deciphering brain chemistry and function. However, this pursuit remains a great challenge. We herein report a neuron‐compatible method for in vivo neurochemical sensing by powering single carbon fiber based on spontaneous bipolar electrochemistry as a new sensing platform. By using ascorbic acid (AA) as a model target to prove the concept, we find that...
Mon Aug 31, 2020 17:54
Hafnium zeolites are shown to catalyse glucose–fructose isomerisation to thermodynamic equilibrium during continuous operation, which no chemical catalyst has yet been able to achieve. Fructose yields of 58 % are observed at a selectivity of 94 %. Structure–activity relationships are developed with X‐ray absorption spectroscopy, chemisorption FTIR, operando UV/Vis and HSQC NMR spectroscopy. Abstract The isomerisation of glucose to fructose is a critical step towards manufacturing petroleum‐free...
Mon Aug 31, 2020 17:45
An efficient non‐conjugated polymer acceptor PF1‐TS4 was developed by embedding thioalkyl linkages in the mainchain of a conjugated polymer. The resulting all‐polymer solar cells achieved a promising device efficiency of 8.63 % with excellent thermal stability at 85 °C for 180 hours. Abstract A non‐conjugated polymer acceptor PF1‐TS4 was firstly synthesized by embedding a thioalkyl segment in the mainchain, which shows excellent photophysical properties on par with a fully conjugated polymer,...
Mon Aug 31, 2020 17:43
A CuCl and anionic chiral cobalt(III) complex co‐catalyzed asymmetric ring‐opening reaction of cyclic diaryliodonium salts was realized. The chiral anion catalysis gave a small size catalytic active copper species, which enabled the cross‐coupling of very bulky aromatic amines. Abstract The present work demonstrates a CuCl and anionic chiral cobalt(III)‐catalyzed enantioselective ring‐opening reaction. The small‐size, ligand‐free copper species enabled the cross‐coupling of iodonium salts...
Mon Aug 31, 2020 17:24
A cocrystal packing arrangement has been tuned from mixed to segregated stack by subtle modulation of halogen bonds from C−Br⋅⋅⋅N to C−I⋅⋅⋅N, giving rise to significantly enhanced radiative decay rate and selectivity. Amplified spontaneous emission characteristics were improved remarkably by cocrystallization, opening up possibilities to the development of organic lasing materials by tailoring multiple radiative decay pathways. Abstract Amplified spontaneous emission (ASE) is intrinsically...
Mon Aug 31, 2020 17:24
Di‐2,7‐naphthihexaphyrin(1.1.1.1.1.1), an expanded carbaporphyrinoid which share structural features of hexaphyrin(1.1.1.1.1.1), incorporates two naphthalene rings. Originally the macrocycle is trapped as two separate, conformationally locked but thermally interconvertible, stereoisomers. Both conformers follow the complex protonation pathways involving structurally different species, which can be targeted under kinetic or thermodynamic control. Abstract Di‐2,7‐naphthihexaphyrin(1.1.1.1.1.1),...
Mon Aug 31, 2020 17:24
An open‐framework semiconductor is demonstrated to have an advantage over its dense‐phase counterpart as high‐performance X‐ray detector due to its optimal balance between resistivity and band gap, as reported by T. Wu and co‐workers in their Research Article (DOI: https://doi.org/10.1002/anie.20201029010.1002/anie.202010290). The image depicts a sulfur‐doped zeolitic In–Se material serving as an excellent X‐ray detector with a high figure‐of‐merit of the mobility‐lifetime product.
Mon Aug 31, 2020 17:00
The De Mayo reaction was employed to fuse the bicyclo[3.2.1]‐octane moiety of ent‐kaurane. Divergent synthesis furnishing ent‐trachylobanes, ent‐beyerane, and ent‐atisane was achieved through nucleophilic cyclopropanation and regioselective cyclopropane fragmentations. Abstract A divergent synthetic approach to biogenetically related diterpenoids such as ent‐kauranes, ent‐trachylobanes, ent‐beyerane, and ent‐atisane has been developed. The unified synthetic route involves the De Mayo reaction...
Mon Aug 31, 2020 16:59
Hybrid hollow architectures composed of highly dispersed Co3O4 hollow nanoparticles embedded in the walls of mesoporous carbon nanoboxes (H‐Co3O4@MCNBs) are synthesized through an elaborate etching‐pyrolysis‐oxidation strategy starting from ZIF‐67 nanocubes. The H‐Co3O4@MCNBs obtained exhibit excellent lithium storage properties as an anode material. Abstract Confining nanostructured electrode materials in porous carbon represents an effective strategy for improving the electrochemical...
Mon Aug 31, 2020 16:58
Amplified FRET Nanoflares: An Endogenous mRNA‐Powered Nanomachine for Intracellular MicroRNA Imaging
An amplified FRET nanoflare can be powered by endogenous mRNA molecules as fuel strands and autonomously work inside living cells without any auxiliary additives. Abstract It is of great value to detect biological molecules in live cells. However, probes for imaging low‐abundance targets in live cells are limited by the one‐to‐one signal‐triggered model. Here, we introduce the concept of the amplified FRET nanoflare, which employs high‐abundance endogenous mRNA as fuel strands to amplify...
Mon Aug 31, 2020 16:58
The template‐assisted assembly of large and emissive carbon quantum dot (CQD) microcrystals using organized amphiphilic cellulose nanocrystals (CNCs) at the liquid–air interface is presented. This large‐scale assembly is facilitated by the complementary amphiphilic interactions of CQDs and CNCs in an organized nematic phase. Abstract Here, we report template‐assisted assembly of emissive carbon quantum dot (CQD) microcrystals on organized cellulose nanocrystals templates at the liquid–air...
Mon Aug 31, 2020 16:57
A new aqueous deep eutectic solvent (DES) electrolyte comprises 9 m MgCl2 and 30 m choline chloride (ChCl). This DES facilitates the reversible insertion of Mg‐Cl superhalides in graphite, where a high reversible capacity of 151 mAh g−1 is delivered. The study reveals the storage mechanism of Mg‐Cl superhalides in graphite, where ordered graphite intercalation compounds (GICs) are not formed. Abstract Oxidative anion insertion into graphite in an aqueous environment represents a significant...
Mon Aug 31, 2020 16:54
110012=52=XXV. Not the answer to everything, but the number of carbons in a sesterterpene, for which we describe the first bacterial type I terpene synthase and geranylfarnesyl diphosphate synthase encoded by a gene cluster from Streptomyces mobaraensis. Seven sesterterpenes were obtained with the recombinant enzymes and their biosynthesis was analyzed by isotope labeling experiments. Abstract A biosynthetic gene cluster from Streptomyces mobaraensis encoding the first cases of a bacterial...
Mon Aug 31, 2020 16:52
An automation platform was designed for glycopeptide synthesis. The automation process is based on chemoenzymatic synthesis and the use of a silica resin and a commercially available peptide synthesizer. The system performs chemical synthesis of peptide in organic solvent, and enzymatic synthesis of glycan epitopes in the aqueous phase using the silica gel resin. Abstract Historically, researchers have put considerable effort into developing automation systems to prepare natural biopolymers...
Mon Aug 31, 2020 16:50
Normally, toxic and caustic fluoride compounds are required for synthesizing the chiral STW‐type zeolite. Now, a fluoride‐free STW synthesis is possible. The roles of fluoride, that is, the formation of a framework rich in tetravalent T‐atoms and promotion of double 4‐membered ring formation, were substituted by dry gel conversion and Ge addition, respectively. Abstract The STW‐type zeolite is attractive for developing novel enantioselective syntheses/separation of chiral compounds because...
Mon Aug 31, 2020 16:49
An iridium pincer complex, immobilized in a microporous polymer network, has been used as an efficient and recyclable catalyst for the gas phase hydrogenation of ethene and propene at room temperature and low pressure. Abstract An iridium dihydride pincer complex [IrH2(POCOP)] is immobilized in a hydroxy‐functionalized microporous polymer network using the concepts of surface organometallic chemistry. The introduction of this novel, truly innocent support with remote OH‐groups enables the...
Mon Aug 31, 2020 16:49
Interaction of a‐Synuclein (aS) with biological lipid is crucial for the onset of its fibrillation at the cell membrane‐water interface. Here, we probe the interaction of aS with membrane mimicking lipid monolayer‐water interfaces using surface‐selective heterodyne‐detected vibrational sum frequency generation (HD‐VSFG) spectroscopy. Our results depict that aS interacts negligibly with zwitterionic lipid, but strongly affects the pristine air‐water and charged lipid‐water interfaces by perturbing...
Mon Aug 31, 2020 16:20
An unprecedented influence of chirality in seeded supramolecular polymerization is demonstrated. Homochiral recognition of enantiomeric monomers results in stereoselective seeded growth of one‐dimensional assemblies with a controlled degree of polymerization and narrow dispersity. Abstract Stereoselective and temporally controlled supramolecular polymerizations are ubiquitous in nature and are desirable attributes for the design of chiral, well‐defined functional materials. Kinetically...
Mon Aug 31, 2020 15:44
A designed [NiFe] H2ase mimic 1 was utilized for H2 evolution under visible light irradiation, while a unique dimer 2 was identified in the catalytic process to serve as a real catalyst for H2 photogeneration with extraordinary performance (TOF 1936 h−1). The unprecedented dimer formation and remarkable performance offer inspiration for the construction of heterobinuclear [NiFe]‐H2ase mimics for artificial H2 photosynthesis. Abstract Inspired by the natural [NiFe]‐H2ase, we designed mimic...
Mon Aug 31, 2020 15:15
A general cascade synthesis of pyrroles from nitroarenes is reported. The process is catalyzed by a heterogeneous cobalt catalyst using either dihydrogen, formic acid, or a CO/H2O mixture as reducing agents. This strategy was applied to the synthesis of biologically active compounds, including (+)‐Isamoltane. Abstract A bifunctional 3d‐metal catalyst for the cascade synthesis of diverse pyrroles from nitroarenes is presented. The optimal catalytic system Co/NGr‐C@SiO2‐L is obtained by pyrolysis...
Mon Aug 31, 2020 15:13
A simple in situ method to control the residual lithium in high‐nickel lithium layered oxide is designed. Residual Li2O (the origin of LiOH and Li2CO3) is preemptively converted into the Li2SO4 thin film by injecting SO2 gas during calcination. This method suppresses the generation of LiOH and Li2CO3 during both synthesis and storage, thereby mitigating slurry gelation and gas evolution and improving cycle stability. Abstract The rampant generation of lithium hydroxide and carbonate impurities,...
Mon Aug 31, 2020 15:13
Due to their low dielectric properties, Coulomb interactions between photoinduced charge carriers lead to robust excitonic effects in polymeric photocatalysts. Such effects not only dominate the mechanisms for energy utilization, but also set limitations to the overall photocatalytic quantum yield. Abstract Owing to the intrinsically low dielectric properties, robust Coulomb interactions between photoinduced electrons and holes lead to dramatically strong exciton effects in polymeric photocatalysts....
Mon Aug 31, 2020 15:11
The colinearity of canonical modular polyketide synthases, which creates a direct link between multienzyme structure and the chemical structure of the biosynthetic end‐product, has become a cornerstone of knowledge‐based genome mining. Here we report genetic and enzymatic evidence for the remarkable role of an enoylreductase in the polyketide synthase for azalomycin F biosynthesis. This internal enoylreductase domain, previously identified as acting only in the second of two chain extension cycles...
Mon Aug 31, 2020 13:19
The investigation and manipulation of cellular processes with subcellular resolution requires non‐invasive tools with spatiotemporal precision and reversibility. Building on the interaction of the photoreceptor PAL with an RNA aptamer, we describe a variation of the CRISPR/dCAS9 system for light‐controlled activation of gene expression. This platform significantly reduces the coding space required for genetic manipulation and provides a strong on‐switch with almost no residual activity in the dark....
Mon Aug 31, 2020 12:44
A wide range of allylic zinc reagents as well as zinc enolates open [1.1.1]propellane to generate zincated bicyclopentanes (BCPs) in a highly regioselective manner. These intermediate zinc reagents are trapped with various electrophiles, giving access to fully functionalized BCPs including a BCP‐analogue of the synthetic opioid pethidine. Abstract We report a range of highly regioselective openings of [1.1.1]propellane with various allylic zinc halides, as well as zinc enolates of ketones,...
Mon Aug 31, 2020 11:57
Bioconjugation methods using visible‐light photocatalysis have emerged as powerful synthetic tools for the selective modification of biomolecules under mild reaction conditions. However, the number of photochemical transformations that allow successful protein bioconjugation is still limited because of the need for stringent reaction conditions. Herein, we report that a newly developed water‐compatible fluorescent photosensitizer Q PEG can be used for visible‐light‐induced cysteine‐specific bioconjugation...
Mon Aug 31, 2020 11:44
Imaging of hypoxia in vivo helps with accurate cancer diagnosis and evaluation of therapeutic outcomes. A PtII metallacage is reported with oxygen‐responsive red phosphorescence and steady fluorescence for in vivo hypoxia imaging and chemotherapy. Abstract Imaging of hypoxia in vivo helps with accurate cancer diagnosis and evaluation of therapeutic outcomes. A PtII metallacage with oxygen‐responsive red phosphorescence and steady fluorescence for in vivo hypoxia imaging and chemotherapy...
Mon Aug 31, 2020 11:35
Dibenzoazacylcooctyne (DBCO) is widely used in strain‐promoted copper‐free click reactions. Reported here is an efficient approach to render a switch in click reactivity of DBCO from azide to amine substrates by using silver catalysts, allowing robust conjugation to peptides, proteins, and living bacteriophages. Moreover, by harnessing the caged acylation reactivity of DBCO, site‐specific conjugation to an IgG antibody was achieved. Abstract Strain‐promoted azide–alkyne cycloaddition using...
Mon Aug 31, 2020 11:35
Oral insulin platforms to address various biological barriers are summarized by O. C. Farokhzad, W. Tao et al. in their Minireview (DOI: https://doi.org/10.1002/anie.20200887910.1002/anie.202008879). Representative advances in facilitating oral insulin delivery are demonstrated, including strategies centered on moieties‐mediated transport, cell‐penetrating peptide‐assisted permeation, smart oral robotics transport, and microenvironment‐responsive release.
Mon Aug 31, 2020 11:33
A novel cyclization strategy mediated by hydroxy aspartic acid ligation was developed to construct malacidin A, a new calcium‐binding antibiotic discovered recently without comprehensive stereochemistry elucidation. Such technique allows facile syntheses of malacidin A and its analogues for establishment of its absolute structure. Abstract The development of novel antibiotics is critical to combating the growing emergence of drug‐resistant pathogens. Malacidin A is a new member of the calcium‐dependent...
Mon Aug 31, 2020 11:33
Through a systematic investigation of pyridine‐based porous organic polymers, structural modifications of the monomer unit were found to create a nanotrap to selectively capture palladium in solution, as reported by Q. Sun, S. Ma and co‐workers in their Research Article (DOI: https://doi.org/10.1002/anie.20200659610.1002/anie.202006596). By creating a stronger complex with palladium through intramolecular hydrogen bonding, this vital element could be extracted through recycling plants and waste...
Mon Aug 31, 2020 11:31
A synthetic method has been developed to realize systematic manipulation of two‐dimensional zeolitic nanosheets stacked in a 3D zeolite. The strategy opens up possibilities in the design of zeolitic nanosheet arrangements whose structure can be tailored for applications in catalysis and separation. Abstract Unit‐cell‐thin zeolitic nanosheets have emerged as fascinating materials for catalysis and separation. The controllability of nanosheet stacking is extremely challenging in the chemistry...
Mon Aug 31, 2020 11:31
The rotational dynamics of single fluorescent dyes are influenced by their surrounding nano‐environment within lipid membranes. In their Research Article (DOI: https://doi.org/10.1002/anie.20200620710.1002/anie.202006207), M. D. Lew and co‐workers show that super‐resolved imaging of molecular orientation and wobble in 3D resolves lipid composition, liquid‐ordered and disordered phases, and enzyme activity in membranes.
Mon Aug 31, 2020 11:30
An artificial quaternary ammonium cation (R4N+) surfactant electrode/electrolyte (E/E) interface construction strategy changes the CO2 reduction reaction (CO2RR) pathway. Molecular dynamics simulations indicate that the artificial interface provided a facile CO2 diffusion pathway. DFT calculations revealed the stabilization of the key intermediates through interactions with R4N+. Abstract In this work, an artificial electrode/electrolyte (E/E) interface, made by coating the electrode surface...
Mon Aug 31, 2020 11:29
The light‐off of the CO oxidation is simultaneous on all Pt crystal surfaces vicinal to the (111) plane, regardless of the reaction conditions, and in contrast with the structural dependence of Pd. Using ambient‐pressure XPS we find that, immediately prior to ignition, atomic oxygen incorporates to the subsurface plane, leading to buckling of the topmost CO‐Pt layer, and effectively equaling the CO desorption temperature at terraces and steps. Abstract The catalytic oxidation of CO on transition...
Mon Aug 31, 2020 11:29
The location and identification of all framework atoms in zeolites, including oxygen bridges, extraframework cations and isomorphous substitution of Si are reported by A. Mayoral, O. Terasaki et al. in their Research Article (DOI: https://doi.org/10.1002/anie.20200612210.1002/anie.202006122). The structures of two important zeolites, Na‐LTA and Fe‐MFI, are studied by using two complementary electron detectors in an aberration‐corrected electron microscope. It is the first direct observation of...
Mon Aug 31, 2020 11:28
CsPbBr3 perovskite nanocrystals are readily shaped into large area 2D photonic crystals by means of nanoimprinting lithography, as shown L. Polavarapu, A. Mihi et al. in their Research Article (DOI: https://doi.org/10.1002/anie.20200615210.1002/anie.202006152). The periodic patterning provides efficient light coupling to the nanocrystal layer, increasing the electric field intensity within the perovskite film and resulting in amplified spontaneous emission (ASE) under lower optical excitation fluences...
Mon Aug 31, 2020 11:27
Mixtures of benzene, cyclohexene, and cyclohexane can be separated through solid‐vapor adsorption by using the activated solids of amide naphthotubes. N−H⋅⋅⋅π interactions are found to play a key role in the adsorption selectivity among the three structurally similar molecules. Abstract Benzene hydrogenation is an important industrial process. The reaction is incomplete, resulting in a mixture of benzene, cyclohexane, and/or cyclohexene that have to be separated before any further reactions....
Mon Aug 31, 2020 11:26
Crystals of a green fluorescent protein chromophore analogue show enhanced fluorescence emission in a plastically deformed mechanically bent state owing to strained molecular packing. Abstract Single crystals of optoelectronic materials that respond to external stimuli, such as mechanical, light, or heat, are immensely attractive for next generation smart materials. Here we report single crystals of a green fluorescent protein (GFP) chromophore analogue with irreversible mechanical bending...
Mon Aug 31, 2020 11:26
The synthesis of a new tetraborylethylene and its application in the preparation of [4+0]‐tetraarylethenes (TAEs) is reported. The divergent and stereoselective synthesis of [3+1]‐, [2+2]‐, and [2+1+1]‐TAEs via multiple couplings of vinylboronates with aryl bromides is demonstrated. The strategies employed complement conventional TAE synthesis methods and could facilitate synthesis of TAE‐based molecules for diverse applications. Abstract The synthesis of a new tetraborylethylene (TBE)...
Mon Aug 31, 2020 11:26
An anionic cascade reaction initiated by an addition of enolate to a non‐activated allene generated in situ has been developed. The formal [2+2] enol–allene cycloaddition cleanly provides functionalized molecular scaffolds with fused six‐, five‐, and four‐membered rings with full diastereoselectivity. Abstract Catalyst‐free addition of ketone enolate to non‐activated multiple C−C bonds involves non‐complementary reaction partners and typically requires super‐basic conditions. On the other...
Mon Aug 31, 2020 11:26
Gaining mechanistic understanding of electrocatalytic processes is usually a challenging task. In their Research Article (DOI: https://doi.org/10.1002/anie.20200949810.1002/anie.202009498), B. J. M. Etzold and co‐workers propose a new facile way to probe the CO2 reduction pathways on copper by employing ionic liquid as a chemical trapping agent, which altered the product spectrum by selective suppressing the formation of ethylene, ethanol, and n‐propanol. Analyzing the altered product spectrum...
Mon Aug 31, 2020 11:25
A moderate and reversible interaction dominated by the π‐backbonding between NO2 and adsorbent was achieved by inserting transition metals into porphyrin metal–organic frameworks. The accommodated Ni and Al‐OH nodes serve as the active NO2 adsorption sites. Abstract Mitigating ambient nitrogen dioxide (NO2) pollution via selective adsorption on porous materials is a promising approach to tackle such an increasingly pressing environmental health issue. However, very few porous adsorbents...
Mon Aug 31, 2020 11:16
Ultrafast UV‐pump/soft‐X‐ray‐probe spectroscopy provides detailed information about dynamical photochemical processes with ultrafast resolution and atomic specificity. Here, the photodissociation of ICN in the 1Π1 excited state is studied. The carbon K‐edge spectral region reveals a rich transient response that provides direct insights into the dynamics of frontier orbitals during the I−CN bond cleavage process. Abstract Ultrafast UV‐pump/soft‐X‐ray‐probe spectroscopy is a subject of great...
Mon Aug 31, 2020 11:16
The covalent functionalization of black phosphorus intercalation compounds (BPICs) with iodomethane has been developed. Starting from BPICs with different amounts of alkali metal the methylation can be achieved in varying functionalization degrees, which can be determined directly by Raman spectroscopy. Abstract A straightforward quantification method to consistently determine the overall functionalization degree of covalently modified two‐dimensional (2D) black phosphorus (BP) by Raman...
Mon Aug 31, 2020 11:15
CO2 hydrogenation selectivity can be tuned by changing the crystal phase of TiO2 or simply changing the metal loadings on anatase‐TiO2 supported Ru catalysts. The essential reason for the distinctly different selectivity is the charge transfer under reaction conditions, probably as a result of hydrogen spillover, which leads to changes in adsorption and activation of intermediate CO. Abstract Tuning CO2 hydrogenation selectivity to obtain targeted value‐added chemicals and fuels has attracted...
Mon Aug 31, 2020 11:14
Simple, illustrative words nicely explain the fundamental characteristics of organometallic compounds and their reactivity. For Group 4 metallocene complexes unusual descriptors like “tuck(ed)‐in”, “merry‐go‐round reaction”, and “sliding”, “migration”, or “tobogganing” have been used. These terms are explained and discussed in detail. Unusual wording is helpful for a better understanding of complex structures and reaction motifs. Abstract Three selected examples for the use of unusual wording...
Mon Aug 31, 2020 11:14
The digold(I) complex [Au2Cl2(Cy2PCH2PCy2)] reacts with 4,4′‐diphenylene diboronic acid to form a triangular macrocyclic complex with twisted Au‐P‐C‐P‐Au groups at the three corners. The synthesis of the complex and its chemical oxidation produced [6]cycloparaphenylene ([6]CPP) in 59 % overall yield. Abstract The digold(I) complex [Au2Cl2(Cy2PCH2PCy2)] reacts with 4,4′‐diphenylene diboronic acid to form a triangular macrocyclic complex with twisted Au‐P‐C‐P‐Au groups at the three corners....
Mon Aug 31, 2020 11:13
An Ag27 cluster‐assembled 2D MOF has been constructed and employed as the catalyst for carboxylative cyclization of propargylamines with CO2. Both the high TON number and broad substrate scope confirm Ag27‐MOF to be an excellent heterogeneous catalyst, making a breakthrough in the use of 2D MOFs as high‐performance catalysts. Abstract Unprecedented double S2− templated Ag27 clusters have been stabilized by 5,10,15,20‐tetra(4‐pyridyl)porphyrin (TPyP‐H2) ligands to afford a robust 2D metal–organic...
Mon Aug 31, 2020 11:12
Production of renewable nitrogen‐containing chemicals (pyrrole and d‐proline) from biomass‐derived furfural is achieved through a procedure combining chemical and biological process. Abstract Production of renewable, high‐value N‐containing chemicals from lignocellulose will expand product diversity and increase the economic competitiveness of the biorefinery. Herein, we report a single‐step conversion of furfural to pyrrole in 75 % yield as a key N‐containing building block, achieved via...
Mon Aug 31, 2020 11:11
The assembly of complex bacterial glycans presenting rare structural motifs and cis ‐glycosidic linkages is significantly obstructed by the lack of knowledge of the reactivity of the constituting building blocks and the stereoselectivity of the reactions in which they partake. We here report a strategy to map the reactivity of carbohydrate building blocks and apply it to understand the reactivity of the bacterial sugars, caryophyllose, a rare C12‐monosaccharide, containing a characteristic tetrasubstituted...
Fri Aug 28, 2020 22:00
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