Bottom-up Growth of Convex Sphere with Adjustable Cu(0)/Cu(I) Interfaces for Effective C2 Production from CO2 Electroreduction.

One challenge confronting the Cu2O catalysts in the electrocatalysis of carbon dioxide reduction reaction (CO2RR) is the reduction of active Cu(I) species, resulting in low selectivity and quick deactivation. In this study, we for the first time introduce a bottom-up growth of convex sphere with adjustable Cu(0)/Cu(I) interfaces (Cux@Cu2O convex spheres). Interestingly, the interfaces are dynamically modulated by varying hydrothermal time, thus regulating the conversion of C1 and C2 products. In particular, the 4 h hydrothermal treatment applied to Cu0.25@Cu2O convex sphere with the favorable Cu(0)/Cu(I) interface results in the highest selectivity for C2 products (90.5 %). In situ Fourier-transform infrared spectroscopy measurements and density functional theory calculations reveal that the Cu(0)/Cu(I) interface lowers the energy barrier for the production of ethylene and ethanol while increasing the coverage of localized *CO adsorbate for increased dimerization. This work establishes a novel approach for transforming the state of valence-sensitive electrocatalysts into high-value energy-related engineering products.

Structural insights into branch site proofreading by human spliceosome.

Selection of the pre-mRNA branch site (BS) by the U2 small nuclear ribonucleoprotein (snRNP) is crucial to prespliceosome (A complex) assembly. The RNA helicase PRP5 proofreads BS selection but the underlying mechanism remains unclear. Here we report the atomic structures of two sequential complexes leading to prespliceosome assembly: human 17S U2 snRNP and a cross-exon pre-A complex. PRP5 is anchored on 17S U2 snRNP mainly through occupation of the RNA path of SF3B1 by an acidic loop of PRP5; the helicase domain of PRP5 associates with U2 snRNA; the BS-interacting stem-loop (BSL) of U2 snRNA is shielded by TAT-SF1, unable to engage the BS. In the pre-A complex, an initial U2-BS duplex is formed; the translocated helicase domain of PRP5 stays with U2 snRNA and the acidic loop still occupies the RNA path. The pre-A conformation is specifically stabilized by the splicing factors SF1, DNAJC8 and SF3A2. Cancer-derived mutations in SF3B1 damage its association with PRP5, compromising BS proofreading. Together, these findings reveal key insights into prespliceosome assembly and BS selection or proofreading by PRP5.

Structural basis of pre-tRNA intron removal by human tRNA splicing endonuclease.

Removal of the intron from precursor-tRNA (pre-tRNA) is essential in all three kingdoms of life. In humans, this process is mediated by the tRNA splicing endonuclease (TSEN) comprising four subunits: TSEN2, TSEN15, TSEN34, and TSEN54. Here, we report the cryo-EM structures of human TSEN bound to full-length pre-tRNA in the pre-catalytic and post-catalytic states at average resolutions of 2.94 and 2.88 Å, respectively. Human TSEN features an extended surface groove that holds the L-shaped pre-tRNA. The mature domain of pre-tRNA is recognized by conserved structural elements of TSEN34, TSEN54, and TSEN2. Such recognition orients the anticodon stem of pre-tRNA and places the 3'-splice site and 5'-splice site into the catalytic centers of TSEN34 and TSEN2, respectively. The bulk of the intron sequences makes no direct interaction with TSEN, explaining why pre-tRNAs of varying introns can be accommodated and cleaved. Our structures reveal the molecular ruler mechanism of pre-tRNA cleavage by TSEN.

Mechanisms of the RNA helicases DDX42 and DDX46 in human U2 snRNP assembly.

Three RNA helicases - DDX42, DDX46 and DHX15 - are found to be associated with human U2 snRNP, but their roles and mechanisms in U2 snRNP and spliceosome assembly are insufficiently understood. Here we report the cryo-electron microscopy (cryo-EM) structures of the DDX42-SF3b complex and a putative assembly precursor of 17S U2 snRNP that contains DDX42 (DDX42-U2 complex). DDX42 is anchored on SF3B1 through N-terminal sequences, with its N-plug occupying the RNA path of SF3B1. The binding mode of DDX42 to SF3B1 is in striking analogy to that of DDX46. In the DDX42-U2 complex, the N-terminus of DDX42 remains anchored on SF3B1, but the helicase domain has been displaced by U2 snRNA and TAT-SF1. Through in vitro assays, we show DDX42 and DDX46 are mutually exclusive in terms of binding to SF3b. Cancer-driving mutations of SF3B1 target the residues in the RNA path that directly interact with DDX42 and DDX46. These findings reveal the distinct roles of DDX42 and DDX46 in assembly of 17S U2 snRNP and provide insights into the mechanisms of SF3B1 cancer mutations.

Electrostatic co-assembly of nanoparticles with oppositely charged small molecules into static and dynamic superstructures.

Coulombic interactions can be used to assemble charged nanoparticles into higher-order structures, but the process requires oppositely charged partners that are similarly sized. The ability to mediate the assembly of such charged nanoparticles using structurally simple small molecules would greatly facilitate the fabrication of nanostructured materials and harnessing their applications in catalysis, sensing and photonics. Here we show that small molecules with as few as three electric charges can effectively induce attractive interactions between oppositely charged nanoparticles in water. These interactions can guide the assembly of charged nanoparticles into colloidal crystals of a quality previously only thought to result from their co-crystallization with oppositely charged nanoparticles of a similar size. Transient nanoparticle assemblies can be generated using positively charged nanoparticles and multiply charged anions that are enzymatically hydrolysed into mono- and/or dianions. Our findings demonstrate an approach for the facile fabrication, manipulation and further investigation of static and dynamic nanostructured materials in aqueous environments.

Morphology control in crystalline nanoparticle-polymer aggregates.

Self-assembly of nanoparticles can be mediated by polymers, but has so far led almost exclusively to nanoparticle aggregates that are amorphous. Here, we employed Coulombic interactions to generate a range of composite materials from mixtures of charged nanoparticles and oppositely charged polymers. The assembly behavior of these nanoparticle/polymer composites depends on their order of addition: polymers added to nanoparticles give rise to stable aggregates, but nanoparticles added to polymers disassemble the initially formed aggregates. The amorphous aggregates were transformed into crystalline ones by transiently increasing the ionic strength of the solution. The morphology of the resulting crystals depended on the length of the polymer: short polymer chains mediated the self-assembly of nanoparticles into strongly faceted crystals, whereas long chains led to pseudospherical nanoparticle/polymer assemblies, within which the crystalline order of nanoparticles was retained.

Ghost imaging based on asymmetric learning.

Ghost imaging (GI) is an unconventional optical imaging method making use of the correlation measurement between a test beam and a reference beam. GI using deep learning (GIDL) has earned increasing attention, as it can reconstruct images of high quality more effectively than traditional GI methods. It has been demonstrated that GIDL can be trained completely with simulation data, which makes it even more practical. However, most GIDLs proposed so far appear to have limited performance for random noise distributed patterns. This is because traditional GIDLs are sensitive to the under-estimation error but robust to the over-estimation error. An asymmetric learning framework is proposed here to tackle the unbalanced sensitivity to estimation errors of GIDL. The experimental results show that it can achieve much better reconstructed images than GIDL with a symmetric loss function, and the structural similarity index of GI is quadrupled for randomly selected objects.

A residual-based deep learning approach for ghost imaging.

Ghost imaging using deep learning (GIDL) is a kind of computational quantum imaging method devised to improve the imaging efficiency. However, among most proposals of GIDL so far, the same set of random patterns were used in both the training and test set, leading to a decrease of the generalization ability of networks. Thus, the GIDL technique can only reconstruct the profile of the image of the object, losing most of the details. Here we optimize the simulation algorithm of ghost imaging (GI) by introducing the concept of "batch" into the pre-processing stage. It can significantly reduce the data acquisition time and create reliable simulation data. The generalization ability of GIDL has been appreciably enhanced. Furthermore, we develop a residual-based framework for the GI system, namely the double residual U-Net (DRU-Net). The imaging quality of GI has been tripled in the evaluation of the structural similarity index by our proposed DRU-Net.

The Many Ways to Assemble Nanoparticles Using Light.

The ability to reversibly assemble nanoparticles using light is both fundamentally interesting and important for applications ranging from reversible data storage to controlled drug delivery. Here, the diverse approaches that have so far been developed to control the self-assembly of nanoparticles using light are reviewed and compared. These approaches include functionalizing nanoparticles with monolayers of photoresponsive molecules, placing them in photoresponsive media capable of reversibly protonating the particles under light, and decorating plasmonic nanoparticles with thermoresponsive polymers, to name just a few. The applicability of these methods to larger, micrometer-sized particles is also discussed. Finally, several perspectives on further developments in the field are offered.

Supramolecular Control of Azobenzene Switching on Nanoparticles.

The reversible photoisomerization of azobenzene has been utilized to construct a plethora of systems in which optical, electronic, catalytic, and other properties can be controlled by light. However, owing to azobenzene's hydrophobic nature, most of these examples have been realized only in organic solvents, and systems operating in water are relatively scarce. Here, we show that by coadsorbing the inherently hydrophobic azobenzenes with water-solubilizing ligands on the same nanoparticulate platforms, it is possible to render them essentially water-soluble. To this end, we developed a modified nanoparticle functionalization procedure allowing us to precisely fine-tune the amount of azobenzene on the functionalized nanoparticles. Molecular dynamics simulations helped us to identify two distinct supramolecular architectures (depending on the length of the background ligand) on these nanoparticles, which can explain their excellent aqueous solubilities. Azobenzenes adsorbed on these water-soluble nanoparticles exhibit highly reversible photoisomerization upon exposure to UV and visible light. Importantly, the mixed-monolayer approach allowed us to systematically investigate how the background ligand affects the switching properties of azobenzene. We found that the nature of the background ligand has a profound effect on the kinetics of azobenzene switching. For example, a hydroxy-terminated background ligand is capable of accelerating the back-isomerization reaction by more than 6000-fold. These results pave the way toward the development of novel light-responsive nanomaterials operating in aqueous media and, in the long run, in biological environments.

Alkali-Assisted Synthesis of Nitrogen Deficient Graphitic Carbon Nitride with Tunable Band Structures for Efficient Visible-Light-Driven Hydrogen Evolution.

A facile synthetic strategy for nitrogen-deficient graphitic carbon nitride (g-C3 Nx ) is established, involving a simple alkali-assisted thermal polymerization of urea, melamine, or thiourea. In situ introduced nitrogen vacancies significantly redshift the absorption edge of g-C3 Nx , with the defect concentration depending on the alkali to nitrogen precursor ratio. The g-C3 Nx products show superior visible-light photocatalytic performance compared to pristine g-C3 N4 .

Carbon Nanosheets: Nitrogen-Doped Porous Carbon Nanosheets Templated from g-C3 N4 as Metal-Free Electrocatalysts for Efficient Oxygen Reduction Reaction (Adv. Mater. 25/2016).

T. Zhang and co-workers report the synthesis of nitrogen-doped porous carbon nanosheets with extremely high nitrogen content and high surface areas using graphitic carbon nitride (g-C3 N4 ) as template, nitrogen source, and porogen. As described on page 5080, the nanosheets exhibit outstanding oxygen reduction catalytic activities which are comparable to commercial Pt/C catalysts in alkaline media.

Nitrogen-Doped Porous Carbon Nanosheets Templated from g-C3 N4 as Metal-Free Electrocatalysts for Efficient Oxygen Reduction Reaction.

Nitrogen-doped porous carbon nanosheets (N-CNS) are synthesized by hydrothermal carbon coating of g-C3 N4 nanosheets followed by high-temperature treatment in N2 . g-C3 N4 serves as a template, nitrogen source, and porogen in the synthesis. This approach yields N-CNS with a high nitrogen content and comparable oxygen reduction reaction catalytic activities to commercial Pt/C catalysts in alkaline media.

pH-Responsive reversible self-assembly of gold nanoparticles into nanovesicles.

A novel system was reported to realize the reversible self-assembly and disassembly of Au nanovesicles (NVs) driven by pH stimuli with commercially available organic molecules, 4-mercaptobenzonic acid (4-MBA) and oleylamine (OL). Through adjusting deprotonation and protonation of 4-MBA, Au NVs demonstrated a good reversible self-assembly behavior. As a proof-of-concept, Rhodamine B was loaded into the vesicles to demonstrate the reversible pH-responsive controlled release.

Well-Dispersed ZIF-Derived Co,N-Co-doped Carbon Nanoframes through Mesoporous-Silica-Protected Calcination as Efficient Oxygen Reduction Electrocatalysts.

A well-dispersed Co,N co-doped carbon nanoframework (Co,N-CNF) with hierarchically porous structure is successfully synthesized from zeolitic imidazolate framework (ZIF) precursors via a mesoporous-silica-protected calcination strategy. By preventing the irreversible fusion and aggregation during the high-temperature pyrolysis step with this protection strategy, the Co,N-CNF exhibits comparable oxygen reduction reaction (ORR) catalytic activity to that of commercial Pt catalysts with the same loading.

Defect-Rich Ultrathin ZnAl-Layered Double Hydroxide Nanosheets for Efficient Photoreduction of CO2 to CO with Water.

Defect-rich ultrathin ZnAl-layered double hydroxide nanosheets are successfully prepared. Under UV-vis irradiation, these nanosheets are superior efficient catalysts for the photoreduction of CO2 to CO with water. The formed oxygen vacancies lead to the formation of coordinatively unsaturated Zn(+) centers within the nanosheets, responsible for the very high photocatalytic activities.

Copper(I) cysteine complexes: efficient earth-abundant oxidation co-catalysts for visible light-driven photocatalytic H2 production.

A copper(i) cysteine complex generated by mixing Cu(ii) ions with cysteine in aqueous solution greatly enhanced the activity of CdSe photocatalysts for H2 production in aqueous solution under visible light excitation. The complex can enhance the H2 evolution rate by as much as 150 times, by acting as an oxidation co-catalyst and increasing charge carrier lifetimes. The copper(i) cysteine complex can also be applied to enhance the H2 production performance of other semiconductor photocatalyst systems, thereby affording a new research direction in the development of co-catalysts for solar hydrogen production.

Ni3+ doped monolayer layered double hydroxide nanosheets as efficient electrodes for supercapacitors.

Ni(3+) doped NiTi layered double hydroxide (NiTi-LDH) monolayer nanosheets with a particle size of ∼ 20 nm and a thickness of ∼ 0.9 nm have been successfully prepared through a facile bottom-up approach. These NiTi-LDH monolayer nanosheets exhibit excellent supercapacitor performance, including a high specific pseudocapacitance (2310 F g(-1) at 1.5 A g(-1)) and long durability compared with bulk LDH, owing to highly exposed conductive Ni(3+) species (NiOOH) which lead to the increased mobility rate of surface charge and electrolyte-transfer. Therefore, this work is expected to take a significant step towards exploring novel 2D monolayer electrode materials with unique physical and chemical properties for applications in energy storage and conversion.

Flower-like CdSe ultrathin nanosheet assemblies for enhanced visible-light-driven photocatalytic H2 production.

Flower-like CdSe architectures composed of ultrathin nanosheets were prepared via a facile solvothermal method. A relationship was established between the solvothermal temperature and the product structure, and thus the photocatalytic activity. When compared with well-studied CdSe quantum dots, the ultrathin nanosheet assemblies exhibited a better photocatalytic H2 evolution activity under visible light irradiation.

A versatile 'click chemistry' route to size-restricted, robust, and functionalizable hydrophilic nanocrystals.

A versatile addition-crosslinking route is developed to transfer various hydrophobic nanocrystals into water. By assembling amphiphilic ligands and then crosslinking through 'click chemistry', a monolayer of polymer forms on the nanocrystal surface, leading to excellent stability and limited increase in hydrodynamic diameter. These nanocrystals can also be further functionalized easily for various applications such as catalysis, bioimaging, and medical therapy.