Liquid state self‐assembly is important for the understanding of the complex structures having been developed in abiogenesis and biogenesis as well as for numerous potential technological applications. Here the first body‐centered cubic liquid crystalline phase with 8‐connected network topology and open octahedral network structure is reported to be formed by dynamic soft self‐assembly of X‐shaped polyphiles with oligo( para ‐phenylene‐ethynylene) cores. The π‐conjugated rods with perfluorinated...
Large and highly emissive crystals from carbon quantum dots (CQD) have been rarely demonstrated because of severe quenching effects of densely packed dots. Here, we report template‐assisted assembly of emissive CQD microcrystals on organized cellulose nanocrystals templates at the liquid‐air interface. We suggest that this large‐scale assembly is facilitated by the complementary amphiphilic character of CQDs and cellulose nanocrystals in organized nematic phase. The resulting large microcrystals...
The digold(I) complex [Au 2 Cl 2 (Cy 2 PCH 2 PCy 2 )] 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.
The 1,4‐Pd shift strategy allows the functionalization of remote C–H bonds that are difficult to reach directly. We report a domino reaction proceeding via C(sp3)–H activation, 1,4‐Pd shift and amino‐ or alkoxycarbonylation, which generates a variety of amides and esters bearing a quaternary β carbon. Mechanistic studies showed that the aminocarbonylation of the σ‐alkylpalladium intermediate arising from Pd shift is fast using PPh3 as the ligand, and leads to the amide rather than the previously...
Organic electroactive compounds are attractive to serve as the cathode materials of aqueous zinc‐ion batteries (ZIBs) because of their resource renewability, environmentally friendliness and structural diversity. Up to now, various organic electrode materials have been developed and different redox mechanisms are observed in aqueous Zn/organic battery systems. In this Minireview, we present the recent developments in the energy storage mechanisms and design of the organic electrode materials of aqueous...
The first total synthesis of cryptotrione ( 1 ) has been achieved through substrate‐controlled diastereoselective construction of the bicyclo[3.1.0]hexene framework via platinum‐catalyzed enyne cycloisomerization, Lewis‐acid induced polyene cyclization to construct the abietane type tricyclic diterpene skeleton, as well as diastereo‐divergent conjugate addition to generate the tertiary carbon center on the side chain.
Measuring tumbling : A stable 13C1‐labeled triarylmethyl radical, whose EPR spectrum is highly sensitive to molecular tumbling, is presented. Owing to the strong anisotropy of the hyperfine coupling tensor, the probe rotational correlation time can be measured. Applications include determining microviscosity and molecular dynamics. Abstract A stable triarylmethyl spin probe whose electron paramagnetic resonance (EPR) spectrum is highly sensitive to molecular tumbling is reported. The strong...
Protected : The pore structure evolution from opened to closed states and a surface wettability transition from hydrophilic to hydrophobic behaviors can be achieved in a smart thermal‐gated PNIPAM/AM‐5@GF separator by increasing the temperature. As a result, zinc‐ion batteries (ZIBs) with such a separator display an excellent thermal‐responsive ability and realize self‐protection of the ZIB by shutting down rapidly at high temperatures. Abstract Smart self‐protection is essential for addressing...
One stone, two birds : The twofold advantages of silver coupling with ordered mesoporous Co3O4 for OER are demonstrated. Metallic silver enhances the conductivity of the structure while Ag2O nanoclusters provide centers for Fe uptake from the KOH electrolyte and boost significantly the efficiency of the electrocatalyst. Abstract Herein, we show that the performance of mesostructured cobalt oxide electrocatalyst for oxygen evolution reaction (OER) can be significantly enhanced by coupling...
Bind and deliver : Cationic oligoproline tightly complexes myo‐inositol hexakisphosphate (InsP6) and delivers this eukaryotic messenger into the cell nucleus. The complexation is enabled by a conformational switch of the PPII‐helical oligoproline upon binding to InsP6. Abstract Inositol hexakisphosphate (InsP6) is a central member of the inositol phosphate messengers in eukaryotic cells. Tools to manipulate the level of InsP6, particularly with compartment selectivity, are needed to enable...
FA detected : A lysine analogue, PrAK, having 2‐aza‐Cope reactivity with formaldehyde (FA), is site‐specifically incorporated into the essential lysine residues of enhanced green fluorescent protein and firefly luciferase by genetic code expansion technology to construct fluorescent and luminescent FA probes, respectively. The probes demonstrate selective detection and imaging of FA in both aqueous buffers and living mammalian cells. Abstract Formaldehyde (FA) is endogenously produced in...
Networking : The Preyssler polyoxoanion, [NaP5W30O110]14− ({P5W30}), was used to evaluate the role of nonbridging cations in the formation of transition‐metal‐bridged polyoxometalate (POM) coordination frameworks. The assembly architecture of Co2+‐bridged frameworks is dependent on the identity and amount of alkali‐ or alkaline‐earth cations present during crystallization. Overall, these results provide insight into factors governing controlled assembly of POM‐based coordination networks. ...
Bringing reactions to light : Mechanically assisted bioluminescence arising from a reaction between luciferase from the small ostracod Cypridina and luciferin can be detected and quantified spectroscopically. This or similar reactions could be used in the future for in situ monitoring of mechanochemical reactions without the need for chemical sampling. Abstract Mechanochemical analogues have recently been established for several enzymatic reactions, but they require periodic interruption...
On the dot : Reported is a facile strategy to control the preparation of the graphdiyne quantum dots which have a high fluorescence quantum yield of up to 42.82 % and exhibit superior dispersibility in many organic solvents and water. The excellent photophysical properties as well as the outstanding biocompatibility, safety, and long‐term photostability makes them candidates for potential optical imaging and biomedical applications. Abstract Graphdiyne (GDY) as an emerging two‐dimensional...
A highly active but extremely O2‐sensitive [FeFe] hydrogenase that acts as a H2‐oxidation catalyst in a H2/O2 biofuel cell is integrated in a shielded bioanode and a membrane‐free H2/O2 biofuel cell. The enzyme was wired to gas diffusion electrodes by means of a viologen‐modified redox polymer matrix. Outstanding current densities of up to 14 mA cm−2 and power outputs of 5.5 mW cm−2 in a membrane‐free device were achieved. Abstract The incorporation of highly active but also highly sensitive...
High‐performance electrocatalysts for the hydrogen evolution reaction (HER) have an important role to play in the development of renewable energy. Despite the enormous efforts to find cheaper alternative materials, platinum remains the most efficient known HER electrocatalyst. Therefore, it is necessary to find ways to maximize Pt utilization in actual practical applications. Here we demonstrate a facile strategy for synthesizing RuCeO x ‐supported selectively loaded atomic Pt (0.49 wt.%) (denoted...
Li‐O 2 batteries with ultrahigh theoretical energy densities usually suffer from low practical discharge capacities and inferior cycling stability owing to the cathode passivation caused by insulating discharge products and by‐products. Here, we firstly introduce a new kind of trifunctional ether‐based redox mediator, 2,5‐di‐tert‐butyl‐1,4‐dimethoxybenzene (DBDMB), into the electrolyte to capture the reactive O 2 ‐ and alleviate the rigorous oxidative environment during cycling of Li‐O 2 batteries....
We report the synthesis of all‐cis 1,2,4,5‐tetrakis (trifluoromethyl)‐ and all‐cis 1,2,3,4,5,6‐hexakis (trifluoromethyl)‐ cyclohexanes by direct hydrogenation of precursor tetrakis‐ or hexakis‐ (trifluoromethyl)benzenes. The resultant cyclohexanes have a stereochemistry such that all of the CF 3 groups are on the same face of the cyclohexyl ring. All‐cis 1,2,3,4,5,6‐hexakis(trifluoromethyl)cyclohexane is the most sterically demanding of the all‐cis hexakis substituted cyclohexanes prepared to date...
Bottom‐up self‐assembled bio‐inspired materials have attracted increasing interest in diverse fields. The use of peptide supramolecular semiconductors for optoelectronic applications is especially intriguing. However, the characteristic thermal unsustainability limits their practical application. Here, we report the thermal sustainability of cyclo‐ditryptophan assemblies up to 680 K. Non‐covalent interactions underlie the stability mechanism, generating a low exciton binding energy of only 0.29 eV...
Catellani reaction has received extensive attentions as it allows rapid multiple derivatization on aromatics. While using alkyl electrophiles to achieve ortho ‐alkylation is one of the earliest features of Catellani reaction, beta ‐H incorporated ipso ‐alkylation terminated reaction has not been realized to date. Herein, we report alkylation terminated Catellani reaction using alkyl carbagermatranes (alkyl‐ Ge ) as nucleophiles. Reactivity of alkyl‐ Ge and alkyl‐B(OH) 2 in this reaction...
The whole electrochemical society is inspired by the first prototype of rechargeable magnesium (Mg) batteries demonstrated two decades ago. However, the development of rechargeable Mg batteries has been hampered by the incompatibility between Mg‐metal anode and conventional electrolytes. Efforts have been made to seek new electrolytes that are thermodynamically stable against reduction at the expense of low oxidation potential at cathode side. Alternatively, using artificial solid‐electrolyte interphase...
Ultrafast UV‐pump/soft‐X‐ray‐probe spectroscopy is a subject of great interest since it can provide detailed information about dynamical photochemical processes with ultrafast resolution and atomic specificity. Here, we focus on the photodissociation of ICN in the 1Π1 excited state, with emphasis on the transient response in the soft‐X‐ray spectral region as described by the ab initio spectral lineshape averaged over the nuclear wavepacket probability density. We find that the carbon K‐edge spectral...
NHC‐boryl radicals are generated by single‐electron oxidation of NHC‐BH3 complexes using a photoredox catalytic system. New reaction modes of NHC‐boryl radicals were determined for the facile synthesis of highly elaborated organoboron molecules. Key: N‐heterocyclic carbene (NHC), leaving group (LG). Abstract Radical borylation using N‐heterocyclic carbene (NHC)‐BH3 complexes as boryl radical precursors has emerged as an important synthetic tool for organoboron assembly. However, the majority...
The development of catalysts that can operate under exceptionally harsh and unconventional conditions is of critical importance for the transition of the energy and chemicals industries to low‐emission and renewable chemical feedstocks. In this review we will highlight materials and more specifically metal‐containing zeolite catalysts that have been tested under harsh reaction conditions such as high temperature light alkane conversion and biomass valorization. Particular attention will be given...
The (formal) replacement of the cobalt‐centre in cobalamin (Cbl) by a Ni(II) generates nibalamin (Nibl), a new type of transition metal analogue of vitamin B12. Here, we describe Nibl, synthesized by incorporation of a Ni(II)‐ion into the complete metal‐free B12‐ligand hydrogenobalamin (Hbl), which was prepared from hydrogenobyric acid (Hby). The related Ni(II)‐corrin nibyric acid (Niby) was similarly synthesized from Hby, the metal‐free cobyric acid ligand. The solution structures of Hbl, as well...
Self‐assembled peptide‐based nanostructures have been widely applied in nanomedicine. However, often their nanoparticle tumor retention time is too limited for efficient drug delivery. Inspired by the dynamic morphology control of molecular assemblies in biological systems, we have developed pH‐responsive transformable peptide‐based nanoparticles for photodynamic therapy (PDT) with prolonged tumor retention times. The self‐assembled peptide‐porphyrin nanoparticles transformed from spheres into nanofibers...
DNA nanotechnology uses oligonucleotide strands to assemble molecular structures capable of performing useful operations. Here, we assembled a multifunctional prototype DNA nanodevice, DOCTR, that recognizes a single nucleotide mutation in a cancer marker RNA followed by cutting out a signature sequence and using it as an activator for a ‘therapeutic’ function: cleavage of another RNA sequence. The proposed design is a prototype for a gene therapy DNA machine that cleaves a housekeeping gene only...
A friend to sodium : A fibrous hydroxylated h‐Ti3C2/carbon nanotubes composite is designed as a scaffold for dendrite‐free Na metal electrodes. It displays fast Na+/electron transport kinetics, high sodiophilicity, and satisfactory thermal conductivity and mechanical properties. Abstract Sodium metal is a promising anode, but uneven Na deposition with a dendrite growth seriously impedes its application. Herein, a fibrous hydroxylated MXene/carbon nanotubes (h‐Ti3C2/CNTs) composite is designed...
Transition metal‐catalyzed enantioselective functionalization of C–H bond, the most abundant functionality in organic molecules, has emerged as an expedient synthetic approach to streamline the synthesis of complex chiral molecules. Despite significant progress, traditional directing group‐enabled strategy requires additional steps for the installation and removal of directing groups from the target molecule. The recent developed asymmetric C–H functionalization using chiral transient directing groups...
Abstract: Aiming for sustainable development, the syntheses of degradable polymers from renewable resources are highly encouraging. Unfortunately, such efforts are deterred by technical and economic challenges; especially, the conversion of natural building blocks to polymerizable monomers is inefficient, requiring multistep synthesis and chromatographic purification. Herein we report a chemoenzymatic process to address these challenges. In this work, a novel enzymatic reaction system was designed,...
Emulating the function of natural carboxylases to convert CO2 under atmospheric condition is a grand challenge. Here we report a class of CO2‐folded single‐chain nanoparticles (SCNPs) that can function as recyclable, function‐intensified carboxylase mimics. Using Lewis pair polymer containing bulky Lewis acidic and basic groups as the precursor, it can bind CO2 to drive an intramolecular folding into SCNP, in which CO2 as the folded nodes can form gas‐bridged bonds. Such bridging linkages highly...
The large paramagnetic shifts and short relaxation times resulting from the presence of a paramagnetic centre complicate NMR data acquisition and interpretation in solution. As a result, NMR analysis of paramagnetic complexes is limited in comparison to diamagnetic compounds and often relies on theoretical models. We report a toolbox of 1D ( 1 H, proton‐coupled 13 C, selective 1 H‑decoupling 13 C, steady‐state NOE) and 2D (COSY, NOESY, HMQC) paramagnetic NMR methods that enables unprecedented...
The isomerisation of glucose to fructose is a critical step towards manufacturing petroleum‐free chemicals from lignocellulosic biomass. Here we show that Hf‐containing zeolites are unique catalysts for this reaction, enabling true thermodynamic equilibrium to be achieved in a single step during intensified continuous operation, which no chemical or biological catalyst has yet been able to achieve. Unprecedented single pass yields of 58 % are observed at a fructose selectivity of 94 %, and continuous...
Non‐ionic polysubstituted azopyrimidines with strong push–pull character are promising candidates for extremely fast photochromic oscillators. The fast oscillation is based on photoinduced (E )‐to‐(Z ) isomerization of the azo group and the accordingly very fast (Z )‐to‐(E ) thermal relaxation. In their Communication (DOI: https://doi.org/10.1002/anie.20200706510.1002/anie.202007065), E. Procházková, M. Cigáň et al. demonstrate how the relaxation lifetime can be tuned by proper substitution over...
Having control : Stimuli‐responsive hydrogels with triggered stiffness properties are attracting growing interest as smart materials for different applications. The Review discusses the design of biomolecule‐based stimuli‐responsive hydrogels and their applications as self‐healing, shape‐memory, and controlled drug‐release matrices, as well as mechanical actuators. Surface‐confined switchable hydrogels and their uses are also introduced. Abstract This Review presents polysaccharides, oligosaccharides,...
The initial C−C bond formation during the early stages of methane dehydroaromatization was investigated by employing “mobility‐dependent” solid‐state NMR spectroscopy. Based on the detected species (such as acetylene, acetal etc.) at least two different mechanisms (mono‐functional vs. bi‐functional) for the formation of direct C−C bonds were identified. Abstract Methane dehydroaromatization (MDA) is among the most challenging processes in catalysis science owing to the inherent harsh reaction...
The crystal‐to‐crystal phase transformation of organic cocrystals under multiple external stimuli, such as solvent vapor and heating, accompanied by reversible luminescent switching, is demonstrated by B. Xu et al. in their Communication (DOI: https://doi.org/10.1002/anie.20200222010.1002/anie.202002220). The results indicate that the luminescence switching originates from the unique molecular rearrangement of a hydrogen/halogen bond‐directed stack to a π–π interaction‐directed stack in response...
The CH–π interactions between the CH donor groups of Trp81‐ζ and Trp81‐η with the aromatic π‐systems of ligand 3 (stylized in blue and green, respectively) are illustrated in the cover picture. The backdrop shows a NMR chemical shift scale into which the Trp81 CH cross peaks are schematically drawn. In the complexed form the CH groups are shifted by up to 2.3 ppm as they are shielded by the aromatic ring systems of the ligand. As explained by G. Platzer, M. Mayer et al. in their Research Article...
An increase in push–pull character of substituted 5‐phenylazopyrimidines accelerates their thermal (Z )‐to‐(E ) isomerization to a sub‐microsecond region. The corresponding half‐life can be tuned by proper substitution over 8 orders of magnitude. Abstract Photochromic systems with an ultrahigh rate of thermal relaxation are highly desirable for the development of new efficient photochromic oscillators. Based on DFT calculations, we designed a series of 5‐phenylazopyrimidines with strong...
Pt‐based electrocatalysts : This Minireview illuminates both the theoretical mechanisms from the viewpoints of active sites exposure and altering the surface electronic structure, which enable enhanced and sustained ORR activity, and the practical methods to achieve them in catalysts, with a focus on size reduction, shape control and core elimination methods. Abstract Pt‐based electrocatalysts are considered as one of the most promising choices to facilitate the oxygen reduction reaction...
The next generation : An enzyme formulation using MOFs as carriers for boosted enzymatic activity and enhanced stability has been created. These MOF carriers can also serve as disintegrating agents that simultaneously release enzymes and their activators during biocatalysis with boosted activities. Abstract An enzyme formulation using customized enzyme activators (metal ions) to directly construct metal–organic frameworks (MOFs) as enzyme protective carriers is presented. These MOF carriers...
Bring it on : The synthesis of the first acylboron was achieved in 2007, which started the exploration on the chemistry and properties of this exotic functional group. Since then, many different applications of acylborons were found, which led to the development of many synthetic methodologies. This Minireview focuses on the challenges and ingenious strategies various researchers have developed over the years to allow access to these versatile molecules. Abstract Acylboron compounds are...
CO2 can do : CO2 makes Li–O2 batteries more stable. On the anode side, CO2 can facilitate the formation of a protective and self‐healing Li2CO3 film, which can expel the H2O and aggressive intermediates during cycling. The cathode and electrolyte are also protected because the O2 − intermediate is captured by CO2 to prevent the formation of 1O2. Abstract The lithium (Li)–air battery has an ultrahigh theoretical specific energy, however, even in pure oxygen (O2), the vulnerability of conventional...
Around the world in 80 scents : Take a bite of fruity Tropicalia, explore the lush greeneries of Bamboo Ketone and dive into the clear waters of Azurone. Stroll through blossoming Nympheal fields and let yourself be carried away with comforting odors from renewable sources, such as rotundone, β‐santalol and Ambrocenide. A report on the past 20 years in the molecular world of odors. Abstract This review is the sequel to the 2000 report on the recent advances in the chemistry of odorants...
A cobalt‐catalyzed domino cyclization/ C−H functionalization of aldehydes is reported. The cascade reaction shows high regio‐, diastereo‐, and enantiocontrol towards enantioenriched heterocycles. The enones are readily diversified to furnish complex spirocycles. Preliminary mechanistic studies are also reported. Abstract We report a cobalt‐catalyzed hydroacylation of 1,6‐enynes with exogenous aldehydes in a domino sequence to construct enantioenriched ketones. The products were obtained...
Down to the atom : Through different imaging methods, electron microscopy can provide direct observation of oxygen atoms and sodium cations, pointing the way for the analysis of the local structure around heteroatoms in zeolite frameworks. The data provide clear evidence of Fe on tetrahedral sites within the MFI zeolite structure, clearly distinguished as single atoms. Abstract Zeolites are becoming more versatile in their chemical functions through rational design of their frameworks....
One hand makes light work : The crystallization‐driven asymmetric self‐assembly (CDASA) of the block copolymers leads to the formation of single‐handed helical nanofibers with controlled length, narrow dispersity, and well‐defined helicity. The helical assembly of the block copolymer induced white‐light emission and intense circularly polarized luminescence (CPL). Abstract Controlling the self‐assembly morphology of π‐conjugated block copolymer is of great interesting. Herein, amphiphilic...
A facile and straightforward top‐down approach for the synthesis of WO3−x dots with tunable oxygen deficiencies and ultrahigh biocompatibility is reported. The unique properties of the WO3−x dots opens up the possibility for electroluminescence to be used in clinics as a co‐reactant with uncompromised high performance and unprecedented low animal toxicity compared with the common commercial co‐reactant. Abstract The exceptional nature of WO3−x dots has inspired widespread interest,...
Self‐healing polyurethane with dynamic oxime–carbamate bonds has been incorporated in perovskite films, as reported by X. Hu, F. Li, Y. Chen et al. in their Research Article (DOI: https://doi.org/10.1002/anie.20200381310.1002/anie.202003813). The polyurethan additive releases mechanical stress and repairs cracks at the grain boundaries. This growth strategy for crystalline semiconductors resembles a broken mirror joined together and enables a new approach for the development of flexible and stretchable...
A change of perspective can allow for surprising views. Water becomes a potent medium for synthesizing highly aromatic compounds when heated to high temperatures. In their Communication (DOI: https://doi.org/10.1002/anie.20200036710.1002/anie.202000367), M. M. Unterlass et al. report the hydrothermal synthesis of two classes of highly conjugated organic polymers, polybenzimidazoles and pyrrone polymers. The cover picture shows an abstraction of a water surface, which looks different from different...
Making burnt bridges passable : A burnt‐bridges DNA walker that employs long RNA transcripts for moving along steps on a DNA‐nanotube path, can operate continuously when an enzymatic strategy is employed which consists of degrading the RNA that block the path through addition of RNase A and subsequently restarting the walking through the use of an RNA inhibitor. Abstract DNA walkers are molecular machines that can move with high precision onthe nanoscale due to their structural and functional...
Solar eBiorefinery: Inspired by natural photosynthesis, biocatalytic photoelectrochemical (PEC) platforms are gaining prominence for the conversion of solar energy into useful chemicals by combining redox biocatalysis and photoelectrocatalysis. Deliberate integration of PEC systems with redox biocatalytic reactions can simultaneously produce valuable chemicals on both electrodes using solar‐powered electrons and water. C. B. Park et al. demonstrate in their Communication (DOI: https://doi.org/10.1002/anie.20200689310.1002/anie.202006893)...
Stimuli‐responsive smart photosensitizer (PS) nanoassemblies that allow enhanced delivery and controllable release of PSs are promising for imaging‐guided photodynamic therapy (PDT) of tumors. However, the lack of high‐sensitivity and spatial‐resolution signals and fast washout of released PSs from tumor tissues have impeded PDT efficacy in vivo. Herein, we report tumor targeting and redox‐responsive megnetofluorogenic PS nanoasssemblies ( NP‐RGD ) via self‐assembly of a cRGD‐ and disulfide‐containing...
The anticancer efficacy of photodynamic therapy (PDT) is limited due to the hypoxic feature of the solid tumors. Herein, we report synergistic PDT/chemotherapy with integrated tandem Fenton reactions mediated by ovalbumin encapsulation for improved in vivo anticancer therapy via an enhanced reactive oxygen species (ROS) generation mechanism. The biodegradable protein nanocapsules show a high co‐encapsulation efficiency for multiple functional reagents including photosensitizer Nile blue with...
RNA‐cleaving deoxyribozymes can serve as selective sensors and catalysts to examine the modification state of RNA. However, site‐specific endonuclease deoxyribozymes that selectively cleave posttranscriptionally modified RNA are extremely rare and their specificity over unmodified RNA is low. In this study, we report that the native tRNA modification N 6 ‐isopentenyladenosine (i 6 A) strongly enhances the specificity and has the power to reconfigure the active site of an RNA‐cleaving deoxyribozyme....
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