Nature employs sulfur switches, i.e. redox‐active disulfides, to kinetically control biological pathways in a highly efficient and reversible way. Inspired by this mechanism we describe here a DNA‐based synthetic nanodevice that acts as a sulfur switch and can be temporally controlled though redox regulation. To do this we rationally designed disulfide DNA strands (modulators) that hybridize to a ligand‐binding DNA nanodevice and act as redox‐active allosteric regulators inducing the nanodevice to...
The therapeutic performance of DNAzyme‐involved gene silencing is significantly constrained by inefficient conditional activation and insufficient cofactor supply. Herein, a self‐sufficient therapeutic nanosystem was realized through the delicate design of DNAzyme prodrugs and MnO2 into a biocompatible nanocapsule with tumor‐specific recognition/activation features. The indocyanine green (ICG)‐modified DNA prodrugs are designed by splitting the DNAzyme and then reconstituting into the exquisite catalyzed...
Divergent tetrazine synthesis : Described is a new strategy for the one‐pot synthesis of 3‐thiomethyltetrazines from carboxylic ester precursors, which provides a platform for the synthesis of unsymmetrical tetrazines through Pd‐catalyzed cross‐coupling and the first catalytic thioether reduction to access monosubstituted tetrazines. Abstract Since tetrazines are important tools to the field of bioorthogonal chemistry, there is a need for new approaches to synthesize unsymmetrical and 3‐monosubstituted...
CO2‐mediated hydrogen storage energy cycle is a promising way to implement the hydrogen economy, but the exploration of efficient catalysts to achieve this process remains challenging. Herein, sub‐nanometer Pd‐Mn clusters were encaged within silicalite‐1 (S‐1) zeolites by a ligand‐protected method under direct hydrothermal conditions. The obtained zeolite‐encaged metallic nanocatalysts exhibited extraordinary catalytic activity and durability in both CO2 hydrogenation into formate and formic acid...
Herein we show that corannulene‐based strained π‐surfaces can be obtained through the use of mechanochemical Suzuki and Scholl reactions. Besides being solvent‐free, the mechanochemical synthesis is high‐yielding, fast, and scalable. Therefore, gram‐scale preparation can be carried out in a facile and sustainable manner. The synthesized nanographene structure carries positive (bowl‐like) and negative (saddle‐like) Gaussian curvatures and adopts an overall quasi‐monkey saddle‐type of geometry. In...
An enantioselective Rh(II)‐catalyzed cyclooligomerization reaction of thiophenes having triazolyl and vinyl substituents at the 2‐ and 4‐positions is studied. Structurally interesting cyclic trimers whose chirality is ascribed only to the orientation of the 2,4‐disubstituted thiophene rings are obtained. A choice of the patterns of 2,4‐disubstitution for the starting thiophene monomer allows production of either of both enantiomers. The observed electronic circular dichroism spectra accord with those...
We report herein a nonbiomimetic strategy for the total synthesis of the plicamine‐type alkaloids, zephycarinatines C and D. The key feature of the synthesis was the stereoselective reductive radical ipso‐cyclization using visible‐light‐mediated photoredox catalysis. This cyclization enabled the construction of a 6,6‐spirocyclic core structure by the addition of the carbon‐centered radical onto the aromatic ring. The biological evaluation of zephycarinatines and their derivatives revealed that the...
Selectivity between 1,2 and 1,4 addition of a nucleophile to an α,β‐unsaturated carbonyl compound has classically been modified by the addition of stoichiometric additives to the substrate or reagent to increase their ‘hard’ or ‘soft’ character. Here, we demonstrate a conceptually distinct approach that instead relies on controlling the coordination sphere of a catalyst with visible light. In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic...
Biomolecular droplets formed through phase separation have a tendency to fuse. The speed with which fusion occurs is a direct indicator of condensate liquidity, which is key to both cellular functions and diseases. Using a dual‐trap optical tweezers setup, we found the fusion speeds of four types of droplets to differ by two orders of magnitude. The order of fusion speed correlates with the fluorescence of thioflavin T, which in turn reflects the macromolecular packing density inside droplets. Unstructured...
Donor/donor carbenes are relatively new in the field of carbene chemistry; applications in C–H and X–H insertion reactions are few in number, but demonstrate exquisite chemo‐ and stereo‐selectivity. Recent reports have shown that C–H, N–H, B–H, O–H, Si–H, Ge–H, Sn–H and P–H insertion reactions are feasible with a variety of transition metal catalysts, both inter‐ and intra‐molecularly. Furthermore, high degrees of diastereo‐ and enantio‐selectivity have been observed in several cases. Methods...
Efficient conversion of solar energy by means of photocatalysis shows huge potential to relieve energy crisis and environmental pollution. However, the unsatisfied conversion efficiency still hinders its practical application. Introduction of external fields can remarkably enhance the photocatalytic performance of semiconductors from the inside out. This review focuses on the recent advances in the diversified external fields, involving the microwave, mechanical stress, temperature gradient, electric...
The hydrogenation of benzaldehyde to benzyl alcohol on carbon‐supported metals in water, enabled by an external potential, is markedly promoted by polarization of the functional groups. The presence of polar co‐adsorbates such as substituted phenols enhances the hydrogenation rate of the aldehyde via two effects–polarizing the carbonyl group and increasing the probability of forming a transition state for H addition. These two effects enable a hydrogenation route, in which phenol acts as a conduit...
A novel low‐symmetry organic molecular cage with distinctive geometry was successfully synthesized from 5,5'‐(propane‐2,2‐diyl)bis(2‐hydroxyisophthalaldehyde) and 1,2‐cyclohexanediamine building blocks, through the desymmetrized vertex design strategy. Single crystal X‐ray crystallographic analysis shows that the cage contains asymmetrical and nonplanar windows, exhibiting an unprecedented C2 symmetry and an efficient packing. The molecular cage structure was also characterized by FT‐IR, NMR, MALDI‐TOF,...
Derivatives based on anthryleno[1,2‐b]pyrazine‐2,3‐dicarbonitrile ( DCPA) are used as luminescent materials, to realize near‐infrared (NIR) electroluminescence. By functionalizing DCPA with aromatic amine donors, two emitters named DCPA‐TPA and DCPA‐BBPA are designed and synthesized. Both molecules have large dipole moments due to the strong intramolecular charge transfer interactions between the amine donors and the DCPA acceptor. Thus, compared with doped films, the emission of neat films...
Fluorescent probes in the second near‐infrared region (NIR‐II, 1000~1700 nm) have resulted in unprecedented imaging performance. Here, we describe a fluorination strategy in semiconducting polymers for development of highly bright NIR‐II probes. Notably, tetrafluorination yielded a fluorescence QY of 3.2% for the polymer dots (Pdots), over 3‐fold enhancement as compared to non‐fluorinated counterparts. The fluorescence enhancement was attributable to nanoscale fluorous effect in the Pdots that maintained...
Spin ice is an exotic type of magnetism displayed by bulk rare‐earth pyrochlore oxides. We discovered a spin ice‐like magnetic relaxation of [{Mn(saltmen)} 4 {Mn(CN) 6 }](ClO 4 )·13H 2 O (saltmen 2− = N,N’ ‐(1,1,2,2‐tetramethylethylene)bis(salicylideneiminate)). This magnetic system can be considered as a two‐dimensional network of Mn III salen‐type single‐molecule magnets (SMMs), in which each SMM unit ( S T = 4) has two orthogonally oriented axial anisotropies and is connected...
Joint catalysis : The cooperative Cu/Pd‐catalyzed four‐component borocarbonylation of vinylarenes, aryl halides/triflates, B2Pin2, and CO generates β‐boryl ketones and β‐boryl vinyl esters in good to high yields. A rational mechanism was proposed for the synthesis of β‐boryl vinyl esters, which involves an acyl‐copper intermediate in the Cu cycle. Abstract We report here a general four‐component synthetic procedure for the preparation of β‐boryl ketones and β‐boryl vinyl esters. Joint catalyzed...
Cobalt phosphide is prepared by atomic layer deposition for the first time. The optimized recipe employs an extra H2 plasma step to remove excess phosphorus. The as‐deposited Co‐P films demonstrate significantly higher activities towards electrochemical and photoelectrochemical hydrogen evolution reaction than that prepared by a traditional method. Abstract Transition‐metal phosphides (TMP) prepared by atomic layer deposition (ALD) are reported for the first time. Ultrathin Co‐P films...
Local structure modulations deviating from ideal framework‐type structures are important fine‐structural features within zeolite frameworks. By using (S)TEM with diffraction and imaging approaches, point, column and planar modulations can be observed in both reciprocal and real space. Abstract Zeolites are widely used in catalysis, gas separation, ion exchange, etc. due to their superior physicochemical properties, which are closely related to specific features of their framework structures....
Cool down : Depending on the cooling rate, a monomeric perylene bisimide equipped with four acyloxy bay substituents self‐assembles into two distinct polymorphs that exhibit distinctive optical properties and packing arrangements. The interchromophoric arrangement was elucidated in the liquid‐crystalline state, demonstrating the effect of homo‐ versus heterochiral self‐sorting, directing self‐assembly into one‐ or two‐dimensional structures, respectively. Abstract A new perylene bisimide...
Pretarget then activate : Functionalization of single‐walled carbon nanotubes (SWCNTs) with tetrazines led to a stable and biocompatible material that undergoes a rapid inverse‐electron‐demand Diels–Alder reaction with trans‐cyclooctene caged molecules. This approach enables bioorthogonal activation of responsive drugs or probes in solid tumours in a strictly controlled manner. Abstract The bioorthogonal inverse‐electron‐demand Diels–Alder (IEDDA) cleavage reaction between tetrazine and...
Weak bonds : Evidence of the presence of weak hydrogen bonds between the highly polarized C−H of chloroform and a carbonyl oxygen atom at room temperature was obtained using ultrafast two‐dimensional infrared spectroscopy (2DIR). The signature of the making and breaking of these weak hydrogen bonds, as well as its approximate 4 ps time scale was derived from the crosspeak growth in the 2DIR spectrum. Abstract Hydrogen bonds (H bonds) play a major role in defining the structure and properties...
Cage to cage : Soluble, porous, and chemically stable quinoline cages are synthesized from salicylimine cages in one post‐synthetic step. The cages show characteristic acidochromic behavior in bulk and solution, and as thin‐films. Abstract Porous shape‐persistent organic cages have become the object of interest in recent years because they are soluble and thus processable from solution. A variety of cages can be achieved by applying dynamic covalent chemistry (DCC), but they are less chemically...
Get a shift on : An enantioselective bifunctional iminophosphorane (BIMP)‐catalysed 1,3‐prototropic shift of structurally diverse β,γ‐unsaturated cyclohexenones is reported. The reaction is high yielding (up to 99 %) in a short time span and proceeds with a high level of selectivity (up to 99 % ee ) on a wide range of substrates. To complement the experimental data, in‐depth computational studies were undertaken, including multivariate linear regression of TS energy. Abstract A bifunctional...
Two is better than one : Commercially available ICH2Bpin reacts with readily prepared vinylboron ate complexes under practical conditions to valuable 1,3‐bis‐(boryl)alkanes. The cascade proceeds through two subsequent 1,2‐metallate rearrangements of boronate complexes, with the second boronate being form in the initial 1,2‐migration step. Abstract A general and efficient approach for the preparation of 1,3‐bis‐(boryl)alkanes is introduced. It is shown that readily generated vinylboron ate...
Dynamic chains in a rigid matrix : While the sphingosine chains of ceramide molecules in the outermost human skin layer were originally assumed to be fully rigid, spectroscopic data reveals that they display a complex dynamic behavior. These new insights will help fine‐tune the molecular model of the skin lipid barrier. Abstract The lipid phase of the uppermost human skin layer is thought to comprise highly rigid lipids in an orthorhombic phase state to protect the body against the environment....
Under UV irradiation, the homocoupling reaction between two alkynyl groups of a surfactant molecule, 1‐alkynyl acid, is effectively catalyzed by CsBr, the byproduct formed during CsPbBr3 perovskite quantum‐dot (PQD) synthesis. This further drives the self‐assembly of PQDs and leads to the formation of 3D perovskite supercrystals. Abstract Herein, we report the facile growth of three‐dimensional CsPbBr3 perovskite supercrystals (PSCs) self‐assembled from individual CsPbBr3 perovskite quantum...
Recent advances in synthesis of germanosilicate zeolites and their post‐synthesis transformations to novel porous materials are reviewed. The structure‐directing effect of Ge allows the synthesis of new zeolite structures with labile Ge−O bonds in aqueous solutions. Abstract Zeolites are one of the most important heterogeneous catalysts, with a high number of large‐scale industrial applications. While the synthesis of new zeolites remain rather limited, introduction of germanium has substantially...
Control of the microstructure like grain orientation, grain boundaries and thickness are crucial for MOF membranes. In the present work, we develop a novel synthesis strategy to prepare highly c‐oriented ZIF‐95 membranes through vapor‐assisted in‐plane epitaxial growth. In a mixed DMF/water vapor atmosphere, in‐plane epitaxial growth of a ZIF‐95 seeds layer is achieved to obtain an oriented and well‐intergrown ZIF‐95 membrane with a thickness of only 600 nm. Demonstrated by both experimental and...
In nanoparticle self‐assembly, the current lack of strategy to modulate orientational order creates challenges in isolating large‐area plastic crystals. Here, we achieve two orientationally distinct supercrystals using one nanoparticle shape, including plastic crystals and uniform metacrystals. Our approach integrates multi‐faceted Archimedean polyhedra with molecular‐level surface polymeric interactions to tune nanoparticle orientational order during self‐assembly. Experiments and simulations show...
Sulfide solid electrolytes are promising for all‐solid‐state batteries, but many of them exhibit poor air stability. Thermodynamic analyses are performed to investigate stability trends and identify promising material systems with desirable moisture and electrochemical stability and also to provide design principles for the development of air‐stable solid electrolytes. Abstract Sulfide solid electrolytes are promising inorganic solid electrolytes for all‐solid‐state batteries. Despite...
A methanol economy will be favored by the availability of low cost catalysts able to selective oxidize methanol to formate. This selective oxidation would allow extracting the largest part of the fuel energy while simultaneously producing a chemical with even higher commercial value than the fuel itself. Here we present a highly active methanol electroxidation catalyst based on abundant elements and with an optimized structure to simultaneously maximize interaction with the electrolyte and mobility...
Analytical methods that allow simultaneous determination of the concentration and enantiomeric composition of small sample amounts and are also compatible with high‐throughput multi‐well plate technology have received increasing attention in recent years. We now introduce a new class of broadly useful small‐molecule probes and a relay sensing strategy that together accomplish these tasks with five classes of compounds including the challenging group of mono‐alcohols ‐ a scope that stands out among...
The use of photo‐energy represents a promising strategy driving endothermic steam (water) reforming and dry (carbon dioxide) reforming of methane (SRM and DRM) to syngas under mild conditions, but it remains a serious challenge of low syngas selectivity. The precise control of each elementary reaction and acquisition of the crucial step at which photo‐irradiation should be applied are indispensable for engineering the product selectivity. Herein, photoassisted SRM and DRM reactions at room temperature...
Water electrolysis offers a promising green technology to tackle the global energy and environmental crisis, but its efficiency is greatly limited by the sluggish reaction kinetics of both the cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER). In this work, by growing amorphous multi‐transition‐metal (cobalt and iron) oxide on two‐dimensional (2D) black phosphorus (BP), we develop a bifunctional electrocatalyst (CoFeO@BP), which is able to efficiently catalyze...
We introduce color‐shifting fluorophores which reversibly switch between a green and red fluorescent form via an intramolecular spirocyclization. The equilibrium of spirocyclization is environmentally sensitive and can be directly measured by determining the ratio of red to green fluorescence, allowing the generation of ratiometric fluorescent probes and biosensors. Specifically, we develop a ratiometric biosensor for imaging calcium ions (Ca 2+ ) in living cells, ratiometric probes for different...
1,3‐Dipoles are commonly used in [3+2] cycloadditions, whereas isoelectronic uncharged dipole variants remain underdeveloped. In contrast to conventional 1,3‐dipoles, uncharged dipole equivalents form zwitterionic cycloadducts, which can be exploited to build further molecular complexity. Herein the first cycloadditions of oxygen‐substituted isocyanates (O‐isocyanates) are studied experimentally and by DFT calculations. This unique cycloaddition strategy allowed access to a novel class of heterocycle—azaoxonium...
Electroorganic synthesis is a promising tool to design sustainable transformations and discover new reactivities. However, the added setup complexity caused by electrodes in the system impedes efficient screening of reaction conditions. Herein, we present a microfluidic platform that enables automated high‐throughput experimentation (HTE) for electroorganic synthesis at a 15‐microliter scale. Two HTE modules are demonstrated, (1) the rapid electrochemical reaction condition screening for a radical‐radical...
Electrochemical nitrogen reduction (NRR) is a clean, facile, and sustainable approach towards ammonia (NH 3 ) production at ambient conditions. However, the inert nature of nitrogen and competitive hydrogen evolution reaction (HER) command it towards sluggish kinetics and poor selectivity. Inspired by the metal‐sulfur (M‐S) linkages in the nitrogenase enzyme, here we show a surface modification strategy to modulate the electronic structure and improve the N 2 availability on the catalytic surface,...
Heterofission, the photophysical process converting an excited singlet state into two triplets on chemically distinct chromophores, offers great potential for a tuning of the optical bandgap and the splitting between singlet and triplet energies, with both fundamental and applied interest. Here, we report the time‐domain observation of heterofission in mixed thin films of the prototypical singlet fission chromophores pentacene and tetracene using excitation wavelengths above and below the tetracene...
Secondary and tertiary alkylamines are privileged substance classes which are often found in pharmaceuticals and other biologically active small molecules. Herein, we report their direct synthesis from alkenes through an aminative difunctionalization reaction enabled by iron catalysis. A family of ten novel hydroxylamine‐derived aminating reagents were designed for the installation of several medicinally relevant amine groups, such as methylamine, morpholine and piperazine, through the aminochlorination...
Supramolecular porous polyelectrolyte membranes are constructed by utilizing water as cross‐linker from a single poly(ionic liquid). Owing the intrinsic dynamic nature of hydrogen bonding, these SPPMs could switch porosity upon thermal stimuli, which is exemplified by dynamically adaptive transparency to thermal fluctuation. Abstract Reversible regulation of membrane microstructures via non‐covalent interactions is of considerable interest yet remains a challenge. Herein, we discover a...
Isolated iridium atoms and subnanometric iridium clusters are regioselectively generated and stabilized in the 10MR window of MWW zeolite for shape‐selective activation of alkanes. Abstract Preparation of supported metal catalysts with uniform particle size and coordination environment is a challenging and important topic in materials chemistry and catalysis. In this work, we report the regioselective generation of single‐site Ir atoms and their evolution into stabilized subnanometric Ir...
An ideal balance has been achieved among nonlinear optical (NLO) effect, birefringence and cut‐off edge for Rb3PbBi(P2O7)2 pyrophosphate. Promising UV NLO materials, Rb3PbBi(P2O7)2 and Cs3PbBi(P2O7)2, were obtained in which [PbPO]∞ layers and BiO6 polyhedra containing two types of lone‐pair cations are present. Abstract Two new pyrophosphates nonlinear optical (NLO) materials, Rb3PbBi(P2O7)2 (I ) and Cs3PbBi(P2O7)2 (II ), were successfully designed and synthesized. Both compounds exhibit...
A molecular design strategy based on frontier molecular orbital engineering (FMOE) has been developed for constructing narrowband green emitters. Combining the advantages of twisted donor–acceptor structure and multiple resonance skeleton has led to an OLED that exhibits a strong narrowband green emission with CIE of (0.23, 0.69) and a maximum external quantum efficiency of 27.0 %. Abstract The design and synthesis of organic materials with a narrow emission band in the longer wavelength...
An in situ bottom‐up confined zeolite crystallization strategy is developed to construct micron‐sized hierarchically ordered macro‐mesoporous single‐crystalline zeolite Beta with improved accessibility to active sites and outstanding (hydro)thermal stability for both gas‐phase and liquid‐phase acid‐catalyzed reactions of bulky molecules. Abstract Zeolite Beta single crystals with intracrystalline hierarchical porosity at macro‐, meso‐, and micro‐length scales can effectively overcome the...
Two isostructural boron‐cluster‐functionalized supramolecular MOFs were rationally designed. They feature suitable pore size and cooperative dihydrogen bonding sites for highly selective capture of acetylene from carbon dioxide and ethylene. Abstract Separation of acetylene (C2H2) from carbon dioxide (CO2) or ethylene (C2H4) is important in industry but limited by the low capacity and selectivity owing to their similar molecular sizes and physical properties. Herein, we report two novel...
Atomic layer deposition derived V2O5 (ALD‐V2O5) as a high‐capacity and stable ZIB cathode is reported. Direct and compelling evidences show that ALD‐V2O5 undergoes an in situ on‐site transformation into nanoscaled Zn3V2O7(OH)2⋅2 H2O (ZVO) and the latter is largely responsible for the excellent electrochemical performance. We also offer our new understanding on the capacity degradation mechanisms. Abstract Developing high capacity and stable cathodes is a key to successful commercialization...
The first adduct of SO to a main group metal system was found by reacting PhNSO with an intramolecular Sn/P frustrated Lewis pair; the exceptional stability of the adduct is attributed to the polarity of the incorporated SO unit. Abstract The geminal frustrated Lewis pair (F5C2)3SnCH2P(tBu)2 (1 ) reacted with N‐sulfinylaniline PhNSO to afford the first sulfur monoxide adduct of a main group metal, (F5C2)3SnCH2P(tBu)2⋅SO (2 ), which contains a SnCPSO ring. The second product is a phenylnitrene...
“The best advice I have ever been given is ‘publish fewer, high‐quality of papers instead of many poor‐quality studies’ … If I won the lottery, I would buy a house for my family and a Jeep Wrangler for myself … ” Find out more about Chen Zhu in his Author Profile.
Carbon encapsulation constitutes a novel concept for improving the stability and tuning the activity of metal catalysts. The key aspects concerning the working principle of this “chain‐mail” approach, as well as the physicochemical properties of the chain mail and metal core that affect the catalytic properties, are considered to highlight directions for applying this strategy in catalyst design. Abstract Encapsulating transition‐metal nanoparticles inside carbon nanotubes (CNTs) or spheres...
Linking molecular and chemical changes to human disease states depends on the availability of appropriate clinical samples, mostly preserved as formalin‐fixed paraffin‐embedded (FFPE) specimens stored in tissue banks. Mass spectrometry imaging (MSI) is an established technique that enables visualization of the spatiotemporal distribution of molecules in biological samples. However, MSI is not effective for imaging FFPE tissues because of the chemical modifications of analytes, including complex crosslinking...
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