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Hydrazone compounds could be highly emissive in the solid state. However, most hydrazone-linking COFs are poorly luminescent. Here we report the enhancement of fluorescence in a 2D hydrazone-linking COF by side chain engineering. Stacking of the bulky and semi-rigid crown ether side chains restricts intramolecular rotation of the backbone around the hydrazone linkers, reducing the thermal dissipation and achieving 20-fold improved emission. [ABSTRACT FROM AUTHOR]

According to Hückel's and Baird's rules, cyclic species are generally aromatic only either in the lowest singlet state (S0) or in the lowest-lying triplet ππ* excited state (T1). Thus, species with aromaticity both in S0 and T1 states (termed as adaptive aromaticity) are particularly rare. Herein, we carry out density functional theory (DFT) calculations to examine the aromaticity of 16e metallapentalenes containing heteroatoms (N, O). Interestingly, metallazapentalenes show adaptive aromaticity whereas metalloxapentalenes display nonaromaticity in the S0 and T1 states, which is supported by structural, magnetic, and electronic indices. In addition, a series of metallazapentalenes containing strong σ- or π-donor ligands are predicted to achieve adaptive aromaticity. Our findings expand the family of adaptive aromatics significantly, inviting experimental chemists to realize more hetero-metallapentalenes with adaptive aromaticity. [ABSTRACT FROM AUTHOR]

The conversion of the ubiquitous greenhouse gas CO2 to valuable organic products is much sought after. Herein, the hydrogenation of CO2 to C1 products with an 80% yield in water is reported using a novel catalyst, porous-silica-supported Au nanoparticles (Au/SiO2). In the presence of a Lewis acid, boric acid, the Au/SiO2 catalyst enables an efficient conversion of amine-captured CO2 to methanol, formate, and formamide. A mechanistic study involving isotopic labelling suggests that methanol production in the catalytic process arises from the direct hydrogenation of formate. Most importantly, this one-pot, two-step process is able to convert CO2 in air at ambient pressures to C1 products in the absence of an organic solvent. Furthermore, the catalyst is readily recycled without further purification or reactivation and shows no significant decrease in catalytic activity after four reaction cycles in a reusability test. [ABSTRACT FROM AUTHOR]

In the past few decades, the construction of discrete supramolecular double-metallacycles has attracted wide interest because of their unique structures and their potential applications in photoelectric materials. Since some progress has been made in this area, it is time to summarize the progress of discrete supramolecular double-metallacycles. In this review, we will briefly introduce the synthetic strategy of discrete supramolecular double-metallacycles. In addition, we will discuss the design principles, preparation methods, optical properties, and functions of these discrete supramolecular double-metallacycles. [ABSTRACT FROM AUTHOR]

Waterborne polyurethane (WPU) based polymeric dyes with anthraquinone chromophores were developed to realize coloring textiles and improve color fastness. The preparation of polymeric dyes through the reaction of 1,4-diamino-2,3-diphenoxyanthraquinone (DV26) and NCO-terminated prepolymer was monitored via UV absorption spectroscopy. With the progress of the reaction, the intensity of the absorption peak of the primary amine group at 586 nm decreased as a function of reaction time. Thus, the conversion of DV26 at different times and the reaction end point could be determined. The reaction mechanism corresponded to an autocatalytic reaction equation, basically. In addition, the results of performance tests showed that the polymeric dyes exhibited good emulsion stability, ultra-low migration percentages, good water resistance and excellent thermal stability. Moreover, the application properties of DWPU on coated polyester fabrics were satisfactory. [ABSTRACT FROM AUTHOR]

As a series of important metal materials, rare earth elements and their related derivative compounds have received significant attention because of their narrow emission bands, noncytotoxicity, excitation of multiple fluorescence colors and electrochemical properties. These unique properties endow rare earth-based nanomaterials with great potential for application in various fields such as in supercapacitors, batteries, sensors, devices and solar cells. This review presents a general description of the electrochemical properties of rare earth-based nanomaterials. The developments and improvements of their electrochemical applications in electrochemical sensors for the detection of small biomolecules and DNA, supercapacitors, batteries and electrochemical catalysis towards the hydrogen evolution reaction have also been discussed. [ABSTRACT FROM AUTHOR]

Near-infrared photothermal-activated nanomaterials are emerging as a promising tool in precise cancer theranostics. This Frontier article highlights the recent advances of photothermal-activated nanoagents in biomedical applications, namely photothermal-initiated drug/contrast agent release, gene silencing, programmed targeting and gas theranostics. In the end, we give a perspective on the further development of photothermal-sensitive nanomedicines. [ABSTRACT FROM AUTHOR]

High-performance SERS chips via self-assembled hollow Ag octahedra on PDMS were employed to achieve the sensitive identification and detection of antibiotic residues. The developed SERS chips were successfully applied in the detection of ciprofloxacin (CIP), amoxicillin (AMX) and cefazolin (CZL) in wastewater and tap water samples, as well as enrofloxacin (ENR) in milk, demonstrating the sensitive determination of antibiotics in the real environment. From this perspective, these SERS chips are expected to expand the on spot sensitive detection and identification field of antibiotic residues. [ABSTRACT FROM AUTHOR]

ZIF-67 derived CoP-decorated nitrogen-doped porous carbon (CoP-NPC) polyhedra anchored on reduced graphene oxide (RGO) sheets have been successfully prepared through an efficient pyrolysis–phosphidation–assembly strategy. The resulting CoP-NPC/RGO composite as an electrode for supercapacitors shows an enhanced electrochemical performance with high capacitances of 466.6 F g−1 at 1 A g−1 and 252 F g−1 at 20 A g−1, as well as 94.7% of capacitance retention after 10 000 cycles in 1 M H2SO4 solution. Moreover, the symmetrical two-electrode device assembled from CoP-NPC/RGO electrodes delivers a high energy density of 12 W h kg−1 at a power density of 500 W kg−1 and excellent long-term cycling stability (93% of the initial capacitance after 10 000 cycles at 10 A g−1). This superior electrochemical performance of CoP-NPC/RGO can be ascribed to its 3D interconnected porous structure and the synergistic effect between CoP and the nitrogen-doped carbon matrix. The unique architecture of the composites can effectively enhance the electrochemical performance by shortening the diffusion distance of electrolyte ions and improving the electrical conductivity and the contact area between active materials and the electrolyte. The excellent electrochemical performances make CoP-NPC/RGO a promising electrode material for high-performance supercapacitors. [ABSTRACT FROM AUTHOR]

In the past few years, the preparation of novel small-molecule fluorescent probes for specific detection and imaging of chemical species inside lysosomes has attracted considerable attention because of their wide applications in chemistry, biology, and medical science. This feature article summarizes the recent advances in the design and preparation of small-molecule fluorescent probes for specific detection of chemical species inside lysosomes. In addition, their properties and applications for the detection and imaging of pH, H2O2, HOCl, O2Ṗ−, lipid peroxidation, H2S, HSO3−, thiols, NO, ONOO−, HNO, Zn2+, Cu2+, enzymes, etc. in lysosomes are discussed as well. [ABSTRACT FROM AUTHOR]

Three-dimensional (3D) nitrogen-doped carbon materials with a hierarchically porous structure are prepared by the introduction of nitrogen-doped carbon spheres (NCS) into the inter-sheet spaces of graphitic carbon nitride nanosheets (g-CN). The as-prepared graphitic carbon nitride/nitrogen-doped carbon sphere (g-CN/NCS) composites present a high nitrogen doping level, a unique hierarchically porous structure, and a high specific surface area of 448 m2 g−1. Such particular features make the g-CN/NCS composite an ideal material for supercapacitor electrodes, which could deliver a large specific capacitance of 403.6 F g−1 at 0.1 A g−1, an excellent rate capability of 220 F g−1 at 10 A g−1, and a high cycling stability with almost 100% capacitance retention after 5000 cycles at 20 A g−1. Furthermore, the g-CN/NCS electrode-based symmetric supercapacitors exhibit a decent energy density of 6.75 W h kg−1 at a power density of 1000 W kg−1. The enhanced performances are mainly attributed to the high nitrogen doping level and the hierarchically porous structure of the 3D structured g-CN/NCS composites, which provide an efficient pathway for transporting ions and electrons, and endow more active sites for electrochemical energy storage. [ABSTRACT FROM AUTHOR]

Metallaaromatics have attracted considerable interest from both experimentalists and theoreticians since the first prediction of metallabenzenes, in which a CH group is replaced by a transition metal fragment. In comparison with monocyclic metallabenzenes and bicyclic metallanaphthalenes, tricyclic metallaanthracenes are quite less developed. Thus, it is urgent to explore synthetic methods for this rare system. Here we report a thorough investigation on the formation of metallaanthracenes from transition metal fluorenyl complexes via density functional theory calculations. We systematically investigate how metal centres, ligands, and substituents affect such a rearrangement. Our results indicate that formation of metallaanthracenes could become thermodynamically and kinetically favourable from transition metal fluorenyl complexes by tuning suitable metal centres, ligands, and substituents, suggesting an unconventional facile way to prepare such rare tricyclic metallaaromatics for experimentalists, which is in sharp contrast to the traditional isomerisation of metallabenzenes to cyclopentadienyl complexes. [ABSTRACT FROM AUTHOR]

An efficient method for the covalent binding of single wall carbon nanotubes (SWCNT) to gold nanorods (AuNR), based on an inverse-electron-demand Diels–Alder (IEDDA) reaction, is established and discussed. This thermally-mild preparation method allows the potential introduction of thermally-labile species to Au–CNT conjugates. This IEDDA approach provides controllable, clean, and facile access to polymer-free organic-soluble AuNR–SWCNT conjugates for potential applications in catalysis, sensing, and electronic devices. [ABSTRACT FROM AUTHOR]

An efficient self-assembled methanoproline–thiourea organocatalyst for the synthesis of optically active 6-isopropyl-3,4-dihydro-pyrimidines via an asymmetric Biginelli reaction was developed, which is superior to the individual precatalyst. A wide range of optically active 6-isopropyl-3,4-dihydropyrimidines with remarkable pharmacological interest was obtained in high yields with excellent enantioselectivities (up to 99% ee). A plausible transition state has been proposed to explain the origin of the activation and the asymmetric induction. [ABSTRACT FROM AUTHOR]

An efficient method to prepare the 18F-labeled tetrazine-derivative [18F]-SiFA-OTz for bioorthogonal radiochemistry was developed. [18F]-SiFA-OTz can be synthesized with a radiochemical yield of 78 ± 5% within 25 min and can quantitatively react with a model strained dienophile, trans-cyclooctenol. [ABSTRACT FROM AUTHOR]

Solution-deposited SnSe and SnS thin films demonstrate excellent electrocatalytic activity toward the triiodide reduction in dye-sensitized solar cells (DSCs), even better than that of the conventional noble Pt electrode used in DSCs. An enhanced photovoltaic efficiency with the maximum value of 9.4% was thus achieved, higher than that with Pt (9.0%). [ABSTRACT FROM AUTHOR]

A novel luminescence probe based on mono-6-amino-β-cyclodextrin (NH2-β-CD) functionalised gold nanoclusters (β-CD-AuNC) was designed for dopamine (DA) detection. The NH2-β-CD molecules were conjugated onto the surface of 11-mercaptoundecanoic acid capped AuNCs (11-MUA-AuNC) via a carbodiimide coupling reaction. The integrity of the β-CD cavities was preserved on the surface of AuNCs and they retained their capability for molecular DA host–guest recognition. DA could be captured by the β-CD cavities to form an inclusion complex in which the oxidised DA could quench the fluorescence of the β-CD-AuNC probe by electron transfer. The probe could be used to quantify DA in the range of 5–1000 nM with a detection limit of 2 nM. This sensitivity was 1–2 orders of magnitude higher than that in previously reported methods. Interference by both ascorbic acid (AA) and uric acid (UA) was not observed. Therefore, the β-CD-AuNC probe could be directly used to determine the DA content in biological samples without further separation. This strategy was successfully applied to a DA assay in spiked human serum samples and it exhibited remarkable accuracy, sensitivity and selectivity. [ABSTRACT FROM AUTHOR]

Electrochemical reduction of carbon dioxide (CO2) or carbon monoxide (CO) to valuable multi-carbon (C2+) products like acetate is a promising approach for a sustainable energy economy. However, it is still challenging to achieve high activity and selectivity for acetate production, especially in neutral electrolytes. Herein, a bioinspired hemin/Cu hybrid catalyst was developed to enhance the surface *CO coverage for highly efficient electroreduction of CO to acetate fuels. The hemin/Cu electrocatalyst exhibits a remarkable faradaic efficiency of 45.2% for CO-to-acetate electroreduction and a high acetate partial current density of 152.3 mA cm−2. Furthermore, the developed hybrid catalyst can operate stably at 200 mA cm−2 for 14.6 hours, producing concentrated acetate aqueous solutions (0.235 M, 2.1 wt%). The results of in situ Raman spectroscopy and theoretical calculations proved that the Fe–N4 structure of hemin could enhance the CO adsorption and enrich the local concentration of CO, thereby improving C–C coupling for acetate production. In addition, compared to the unmodified Cu catalysts, the Cu catalysts functionalized with cobalt phthalocyanine with a Co–N4 structure also exhibit improved acetate performance, proving the universality of this bioinspired molecule-enhanced strategy. This work paves a new way to designing bioinspired electrolysis systems for producing specific C2+ products from CO2 or CO electroreduction. [ABSTRACT FROM AUTHOR]

Chemical mechanism (CM)-related surface-enhanced Raman spectroscopy (SERS) has received tremendous interest due to its exceptional stability and excellent uniformity. Nevertheless, there remains a demand for ingenious methodologies for promoting effective charge transfer (CT) to improve SERS sensitivity further. Herein, a band structure engineered W18O49/g-C3N4 heterostructure (WCN) was first employed as a CM-based SERS substrate with remarkable enhancement and sensitivity. To investigate the Raman enhancement properties of the substrate, malachite green (MG) was employed as the Raman probe with the excitation of a 633 nm laser. The WCN substrate exhibits a Raman enhancement factor (EF) of 2.6 × 107, achieving a limit of detection (LOD) of 1.9 × 10−10 M for MG. The outstanding Raman amplification behavior can be attributed to the heterojunction-induced efficient CT process, energy band matching resonance due to minor doping with g-C3N4 serving as a band gap modifier, and improved photo-induced charge transfer (PICT) efficiency via the oxygen vacancies in the W18O49 units. Additionally, a flexible SERS substrate based on WCN was constructed using a vacuum filtration method and utilized to detect prohibited pharmaceutical residues on fish skin. The integration of this WCN and a nylon membrane not only preserves the Raman activity of the WCN for sensitive detection but also endows the Raman substrate with high flexibility and good mechanical durability, making it a potential candidate for in situ detection in particular environments. [ABSTRACT FROM AUTHOR]

As a fundamental concept in chemistry, aromaticity has been extended from traditional organics to organometallics. Similarly, hyperconjugative aromaticity (HCA) has also been developed from main group to transition metal systems through the hyperconjugation of the substituents. However, it remains unclear that how the oxidation state of transition metal in the substituents affects the HCA. Herein, we demonstrate via density functional theory calculations that HCA could disappear in indoliums when the Au(I) substituents are changed to the Au(III) ones. By tuning the ligand or cis–trans isomerization, HCA could be regained or enhanced in indoliums containing Au(III) substitutents. [ABSTRACT FROM AUTHOR]

The first Zintl cluster containing a distorted Bi6 triangular prism, [Bi6Mo3(CO)9]4−, has been synthesized and structurally characterized. Quantum chemical calculations indicated that the distorted cage cluster features multiple local σ-aromaticity. [ABSTRACT FROM AUTHOR]

Design and fabrication of cost-effective (pre-)catalysts are important for water splitting and metal–air batteries. In this direction, various metal–organic frameworks (MOFs) have been investigated as pre-catalysts for oxygen evolution. However, the activation process and the complex reconstruction behaviour of these MOFs are not well understood. Herein, square-like MOF nanosheets in which carbon nanotubes were embedded were prepared by introducing an amine ligand to coordinate with Ni ions and then reacting with [Fe(CN)6]3−. The formed MOF nanosheets containing nickel and iron species were then activated by NaBH4, inducing the leaching of ligands and the formation of tiny active species in situ loaded on carbon nanotubes. The prepared catalyst shows superior oxygen evolution performance with an ultralow overpotential of 231 mV for 10 mA cm−2, a fast reaction kinetics with a small Tafel slope of 52.3 mV dec−1, and outstanding catalysis stability. The excellent electrocatalytic performance for oxygen evolution can be attributed to the structural advantage of in situ derived small sized active species and one-dimensional conductive networks. This work provides a new thought for the enhancement of the electrocatalytic performance of MOF materials. [ABSTRACT FROM AUTHOR]

Baird's rule has been applied to a large scope of organic molecular systems for rationalizing the aromaticity reversal in the lowest-lying triplet state. In this study, we demonstrate that Baird's rule can also be extended to all-metal systems with σ- and π-aromaticity. [ABSTRACT FROM AUTHOR]

A series of bifunctional phase-transfer catalysts with a quaternary onium center and a hydrogen-bonding donor group were prepared for the fixation of CO2 with commercially available epoxides under mild conditions by using a CO2 balloon (1 atm). In the presence of 2.5 mol% of achiral bifunctional phase-transfer catalysts, cyclic carbonates were obtained in good to excellent yields (up to 95%). Additionally, optical carbonates and epoxides were obtained through the kinetic resolution of rac-epoxides by 1 mol% of chiral bifunctional phase-transfer catalysts with low enantioselectivities. These catalysts featured a simple synthetic route, good modularity and high efficiency. [ABSTRACT FROM AUTHOR]

An acid-driven separable nanodevice was designed for multilayer imaging of diverse biomarkers with different spatial distributions in living cells. The proposed nanodevice can simultaneously perform in situ imaging of the intracellular microRNAs and extracellular pH, affording a new approach to develop a precise imaging system for disease diagnosis. [ABSTRACT FROM AUTHOR]

Lipases are ubiquitous enzymes of great physiological significance that have been used extensively in multiple industries. Environmental microorganisms are a major source for the discovery of novel lipases with high catalytic efficiency and selectivity. However, current plate-based screening of lipase-producing strains is time consuming, labour intensive and inefficient. In this study, we developed an ultra-high throughput screening pipeline for lipase-producing strains based on fluorescence-activated droplet sorting (FADS) using a compact optical system that could be easily set up in an alignment-free manner. The pipeline includes droplet generation, droplet incubation, picoinjection of the fluorescence probe, and sorting of droplets with a throughput of 2 × 106 drops per h. We applied the pipeline to screen samples collected from different locations, including sediments from a hot spring in Tibet, soils from the Zoige wetland, contaminated soils from an abandoned oilfield, and a Chinese Daqu starter. In total, we obtained 47 lipase-producing bacterial strains belonging to seven genera, including Staphylococcus, Bacillus, Enterobacter, Serratia, Prolinoborus, Acinetobacter, and Leclercia. We believe that this FADS-based pipeline could be extended to screen various enzymes from the environment, and may find wide applications in breeding of industrial microorganisms. [ABSTRACT FROM AUTHOR]

The development of hydrogen–oxygen fuel cells with an alkaline electrolyte was highly limited by the sluggish kinetics of the hydrogen oxidation reaction (HOR). Here, with a pyrolysis-reduction route, a new RuNi-based electrocatalyst was prepared, which presents an ultrathin nanowire-like structure. In alkaline media, this catalyst shows an excellent catalytic performance with an exchange current density of 1.10 mA cm−2disk for hydrogen oxidation. The exchange current density and mass activity of this catalyst are much higher than those of its single-metal counterparts and even the commercial Pt/C catalyst containing 20% Pt. Such a remarkable catalytic activity can be explained by the interaction between Ru and Ni; the incorporation of Ni may induce an electronic effect on the optimization of the Ru–Had strength and provide a functional surface that can absorb OH species, thus boosting the catalytic activity. These findings may cast a new light on the exploration of low-cost but high-efficiency catalysts for fuel cells. [ABSTRACT FROM AUTHOR]

Electrochemiluminescence (ECL) is produced by chemiluminescence reactions initiated by electrochemical methods. On this basis, ECL microscopy (ECLM) is an emerging visualization tool to directly study local electrochemical features with good spatial and temporal resolution. Recent progress in ECLM demonstrates that it is particularly important in single-cell studies on the morphological structures and functional characteristics of cells due to the unique heterogeneity of cells. Compared with other single-cell imaging methods, ECLM possesses advantages such as a low optical background, high sensitivity, simple instrumentation and surface-confined mode. In this mini-review, we discuss the recent development of single-cell ECLM and classify these works according to different ECL routes. Because ECL routes significantly influence the features of ECLM, such as the thickness of the emitting layer and the brightness of emitters, it is necessary to provide a new insight to revisit these works and discuss what ECL routes can be chosen to study single-cell processes from different perspectives. Considering the gradual growth in single-cell ECLM, we show the developmental trajectory and how these works connect with one another. In addition, the coexisting challenges as well as opportunities inspire us to design more ECLM methods to investigate local electrochemical phenomena. [ABSTRACT FROM AUTHOR]

Metal nanoclusters (MeNCs), composed of a few to hundreds of metal atoms and appropriate surface ligands, have attracted extensive interest in the electrochemiluminescence (ECL) realm owing to their molecule-like optical, electronic, and physicochemical attributes and are strongly anticipated for discrete energy levels, fascinating electrocatalytic activity, and good biocompatibility. Over the past decade, huge efforts have been devoted to the synthesis, properties, and application research of ECL-related MeNCs, and this field is still a subject of heightened concern. Therefore, this perspective aims to provide a comprehensive overview of the recent advances of MeNCs in the ECL domain, mainly covering the emerged ECL available MeNCs, unique chemical and optical properties, and the general ECL mechanisms. Synthesis strategies for desirable ECL performance are further highlighted, and the resulting ECL sensing applications utilizing MeNCs as luminophores, quenchers, and substrates are discussed systematically. Finally, we anticipate the future prospects and challenges in the development of this area. [ABSTRACT FROM AUTHOR]

We report a DNA origami cipher disk (DOCD) allowing random, continuous and reversible switchover between six visibly different patterns in response to the input DNA strands. A DOCD-enabled tandem-in-time cryptographic protocol was thereby established by using a string of DNA strands as a carrier for accurate information encoding and transmission. [ABSTRACT FROM AUTHOR]

A fluorogenic RNA aptamer nanodevice integrating an entropy-driven RNA amplifier with near-infrared (NIR) light control was developed, affording high contrast and sensitivity for imaging low-abundance mRNA in living cells. The design principle offers a new approach for developing low-background imaging systems for live-cell studies and manipulation. [ABSTRACT FROM AUTHOR]

Osmapentalyne and osmapentalene complexes, now termed as carbolong species, have attracted considerable attention due to their novel structures, reactivities, and chelating properties as well as Möbius and adaptive aromaticity. On the other hand, boron monofluoride (BF), a 10-electron diatomic molecule isoelectronic to carbon monoxide (CO), is unstable below 1800 °C in the gas phase, and preparation of its metal complex is particularly challenging. Although the iron complex featuring a terminal BF ligand was synthesized recently, the structure, bonding and aromaticity of metallapentalyne and metallapentalene complexes containing BF ligands remain unclear. Herein, we carry out density functional theory (DFT) calculations to address this issue. The Os–B bond could be considered as a single, double or triple bond depending on the ligands attached to the metal center according to principal interacting orbital (PIO) analysis. The similarity on aromaticity is revealed between CO complexes and BF ones. All these species display aromaticity in the S0 state. For the T1 state, they could be aromatic, nonaromatic or antiaromatic depending on the excitation mode. All these findings could be useful to develop the concept of adaptive aromaticity as well as BF chemistry. [ABSTRACT FROM AUTHOR]

We report the straightforward synthesis of ATP-responsive nanoscale metal azolate framework-7 (MAF-7) for gene/drug codelivery. The MAF-7 functions as (i) the armour to preserve DNAzymes, (ii) an ATP scavenger to lower the intracellular ATP level, and (iii) a built-in Zn2+ arsenal to initiate the biocatalysis of DNAzymes, ultimately inhibiting P-gp expression to enhance chemotherapy. [ABSTRACT FROM AUTHOR]

Self-assembled nanomaterials (SANs) exhibit designable biofunctions owing to their tunable nanostructures and modifiable surface. Various constituent units and multi-dimensional structures of SANs provide unlimited possibilities for numerous applications. This review emphasizes the recent development of SANs in the fields of biosensing, bioimaging, and nano-drug engineering. The unit type, design concepts, material advantages, assembly driving force, nanostructure effects, drug loading performance, etc. are discussed and summarized. Finally, we briefly summarize how to assemble unique nanomaterials and point out the key challenges in this field. [ABSTRACT FROM AUTHOR]

Catalytic route electrochemiluminescence (ECL) microscopy enables imaging upper cell membranes with freely diffusing Ru(bpy)32+ as the emitter and nitrogen-doped carbon dots as the nano-coreactants and labels. This strategy provides a vertical resolution when studying the ECL profiles at different heights and realizes the ECL imaging of the externalized phosphatidylserine. [ABSTRACT FROM AUTHOR]

Disilene has attracted considerable interest due to the trans-bending geometry which is significantly different from the planar alkene. However, the equilibrium between disilene and isomeric silylsilylene has not been fully understood. Here, we report a density functional theory (DFT) study on this equilibrium. Calculations reveal significant effects of substituent, aromaticity and base. Specifically, the parent disilene is thermodynamically more stable than the isomeric silylene. When the methoxy substituent is introduced, the corresponding silylene becomes thermodynamically more stable, which could be rationalized by the Bent's rule. Interestingly, disilabenzene becomes thermodynamically more stable than the isomeric silylene when the concept of aromaticity is taken into account. Finally, once the base is introduced, the silylene could become thermodynamically more stable than the isomeric disilabenzene. The kinetic effect of the tautomerization with several typical substituents (F, Me and OMe) has also been investigated. Some species with a bridged form have been found to have a higher thermodynamic stability over the nonbridged ones. All these findings could be particularly useful to develop the chemistry of disilenes and silylenes. [ABSTRACT FROM AUTHOR]

Anisotropic films composed of aligned CsPbBr3 nanowires (NWs) have been successfully fabricated using a mechanical rubbing method. The films with a dense and uniform morphology show polarization photoluminescence (PL) behavior. Combined with an optimal device structure, a polarized light-emitting diode (LED) with a turn-on voltage as low as 6.5 V was obtained. [ABSTRACT FROM AUTHOR]

An effective electrophilic annulation reaction of azacyclic ynones was reported, divergently affording various functionalized 3-iodo-2H-quinolizin-2-ones and 1,3-diiodo-2H-quinolizin-2-ones in moderate to excellent yields with different iodide reagents. This reaction shows high regioselectivity and broad substrate scope under metal-free, room temperature conditions in air. In addition, the products with highly active C–I bonds have an opportunity for further functionalization. [ABSTRACT FROM AUTHOR]

DNA nanotechnology engineered at the solid–liquid interface has advanced our fundamental understanding of DNA hybridization kinetics and facilitated the design of improved biosensing, bioimaging and therapeutic platforms. Three research branches of DNA nanotechnology exist: (i) structural DNA nanotechnology for the construction of various nanoscale patterns; (ii) dynamic DNA nanotechnology for the operation of nanodevices; and (iii) functional DNA nanotechnology for the exploration of new DNA functions. Although the initial stages of DNA nanotechnology research began in aqueous solution, current research efforts have shifted to solid–liquid interfaces. Based on shape and component features, these interfaces can be classified as flat interfaces, nanoparticle interfaces, and soft interfaces of DNA origami and cell membranes. This review briefly discusses the development of DNA nanotechnology. We then highlight the important roles of structural DNA nanotechnology in tailoring the properties of flat interfaces and modifications of nanoparticle interfaces, and extensively review their successful bioapplications. In addition, engineering advances in DNA nanodevices at interfaces for improved biosensing both in vitro and in vivo are presented. The use of DNA nanotechnology as a tool to engineer cell membranes to reveal protein levels and cell behavior is also discussed. Finally, we present challenges and an outlook for this emerging field. [ABSTRACT FROM AUTHOR]

Bifunctional supramolecular prodrug vesicles have been successfully constructed based on the complexation between a glutathione (GSH)-responsive prodrug guest molecule (DNS-CPT) and a water-soluble pillar[5]arene (WP5) for cancer diagnosis and therapy. Under the microenvironment of cancer cells with high GSH concentration, 7-ethyl-10-hydroxycamptothecin (SN-38) with strong yellow fluorescence can be efficiently released from the prodrug DNS-CPT for drug location and cancer therapy. [ABSTRACT FROM AUTHOR]

A microRNA (miRNA) fluorescence (FL) nanoprobe based on PDA-UCNPs@FAM-LLD@AuNPs was developed, which exhibited an enhanced signal for imaging intracellular miRNA by combining double-channel exciting single colour FL (DCESCF) with the target cycling amplification reaction. Through this strategy, normal cells and cancer cells could be successfully discriminated. [ABSTRACT FROM AUTHOR]

The synergistic effect of two anticancer drugs can significantly overcome the multidrug resistance of tumor cells and improve the drug bioavailability. Herein, two different anticancer drugs, camptothecin and chlorambucil, are successfully connected together by a disulfide linkage to get a novel drug–drug conjugated prodrug (G). Using water-soluble pillar[6]arene (WP6) as a host molecule, a supramolecular host–guest complex WP6⊃G is formed, which can further self-assemble into supramolecular vesicles in aqueous solution. In the specific microenvironment of cancer cells, the disulfide linkage is destroyed and the two anticancer drugs can be released efficiently to achieve a better synergistic effect than a single anticancer drug. Notably, these prodrug nanocarriers can not only effectively kill the cancer cells but also obviously reduce the undesirable side effects on normal cells. [ABSTRACT FROM AUTHOR]

A ten times enhanced H2 evolution from the hydrolysis of ammonia borane was realized through bilateral-like plasmonic WO3−x nanorods coupled with Ni2P nanoparticles compared to Ni2P, which provides a new strategy to develop non-noble metal based plasmonic configurations for diverse energy and environment related applications. [ABSTRACT FROM AUTHOR]

A cancer cell-specific, endogenous H+/H2O2-activated, and O2 self-sufficient nanocomposite is engineered and characterized. Such NPs, with good biocompatibility and rapid response to intracellular H+/H2O2, have demonstrated improved therapeutic effects in targeted cancer cells and activated MR signals in vitro, providing a promising strategy for effective PDT against tumor hypoxia. [ABSTRACT FROM AUTHOR]

A new visible-light-assisted microbial fuel cell composed of a three-dimensional nitrogen-doped graphene self-standing sponge anode and a photoresponsive cathode has been developed for achieving multiple energy conversion and a higher power output. [ABSTRACT FROM AUTHOR]

Commercially available NaOH powder is shown to be an efficient transition-metal-free initiator for the catalytic hydroboration of aldehydes, ketones, alkynes and alkenes with HBpin and 9-BBN under mild conditions. Combined experimental and theoretical studies suggest that the catalytically active species is a boron hydride generated in situ from the reaction mixture. [ABSTRACT FROM AUTHOR]

During the past decade, biofuel cells (BFCs) have emerged as an emerging technology on account of their ability to directly generate electricity from biologically renewable catalysts and fuels. Due to the boost in nanotechnology, significant advances have been accomplished in BFCs. Although it is still challenging to promote the performance of BFCs, adopting nanostructured materials for BFC construction has been extensively proposed as an effective and promising strategy to achieve high energy production. In this review, we presented the major novel nanostructured materials applied for BFCs and highlighted the breakthroughs in this field. Based on different natures of the bio-catalysts and electron transfer process at the bio-electrode surfaces, the fundamentals of BFC systems, including enzymatic biofuel cells (EBFCs) and microbial fuel cells (MFCs), have been elucidated. In particular, the principle of electrode materials design has been detailed in terms of enhancing electrical communications between biological catalysts and electrodes. Furthermore, we have provided the applications of BFCs and potential challenges of this technology. [ABSTRACT FROM AUTHOR]

N-heterocyclic ylide-like germylene effectively promotes the hydroboration of aldehydes and ketones under mild conditions with broad substrate tolerance, operational simplicity of procedure and excellent yields. A key intermediate in this catalytic system featuring a bicyclo[2,2,2]octane-like core has been successfully isolated and characterized, suggesting a new type of mechanism that involves the activation mode that mimics that of transition metal catalysts. [ABSTRACT FROM AUTHOR]