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Ti3C2Tx, as a member of the two-dimensional (2D) MXene family, is subject to severe self-restacking due to van der Waals forces between the surfaces of the nanosheets, which limits its application in supercapacitors. In addition, Ti3C2Tx always stores electrical energy non-Faradaic, resulting in a low specific capacitance about 100 F g–1 in basic electrolytes. In this work, we report conductive bismuth-catecholate metal–organic frameworks (Bi-(HHTP)) with one-dimensional (1D) channels grown on the surfaces of 2D Ti3C2Tx nanosheets (Ti3C2Tx/Bi-(HHTP)) for supercapacitors. In the hybrid structure, conductive Bi-(HHTP) serves not only as the spacers to relieve the self-stacking of Ti3C2Tx nanosheets but also as the active component to provide battery-type capacitance. Meanwhile, Ti3C2Tx nanosheets provide skeletons for the conductive Bi-(HHTP), further enhancing the overall specific capacitance of Ti3C2Tx/Bi-(HHTP). By taking advantage of appropriate porosity, redox activity, and good properties of charge transport of Bi-(HHTP), the specific capacitance of Ti3C2Tx nanosheets is significantly increased. The Ti3C2Tx/Bi-(HHTP) electrode obtained exhibits an impressive specific capacitance of 326 F g–1 at 0.5 A g–1 and a good rate capacity of 52%. Additionally, an asymmetric device is assembled with a Ni-(OH)2 cathode and a Ti3C2Tx/Bi-(HHTP) anode, demonstrating remarkable performance with a maximum specific energy of 22.3 Wh kg–1 and a maximum specific power of 11.2 kW kg–1. This work presents a promising strategy for developing high-performance supercapacitor electrodes based on Ti3C2Tx, offering potential avenues for enhancing performance in energy storage applications. [ABSTRACT FROM AUTHOR]

Rational design of a hierarchical core–shell structured photocatalyst is crucial for enhancing the separation and transport efficiency of photogenerated carriers, thereby improving the photocatalytic degradation efficiency. In this study, hollow polyhedral CoSx was first synthesized by utilizing dodecahedral Co-based metal–organic framework (ZIF-67) as a Co source and template, followed by introducing In and S species to fabricate hierarchical core–shell In2S3/CoSx composites. The resulting In2S3/CoSx porous hollow heterostructured composites exhibited an accelerated interfacial carrier transfer ratio and enhanced photocatalytic removal performance of tetracycline hydrochloride (TCH). Among them, the optimized sample In2S3/CoSx-2 (CoIS-2) demonstrated the highest TCH removal rate of 0.0324 min–1, which was 22.8 times higher than that of pristine CoSx and 5.7 times higher than that of pure In2S3, respectively. Moreover, its apparent quantum efficiency reached 4.66% at 420 nm. Electron spin resonance analysis and active substance capture experiments confirmed that superoxide radical (•O2–) played a predominant role in the reaction system. Furthermore, we investigated the dynamics of photoinduced carriers through a series of photoelectric tests combined with density functional theory calculations. This study provides valuable insights into controllable construction of metal–organic framework-based materials with high photocatalytic degradation efficiency and stability. [ABSTRACT FROM AUTHOR]

Human Hint1 suppresses specific gene transcription byinteracting with the transcription factor MITF in mast cells. Hint1activity is connected to lysyl-tRNA synthetase (LysRS), a member ofthe universal aminoacyl tRNA synthetase family that catalyzes specificaminoacylation of their cognate tRNAs, through an aminoacyl adenylate(aa-AMP) intermediate. During immune activation, LysRS produces aside-product diadenosine tetraphosphate (Ap4A) from thecondensation of Lys-AMP with ATP. The pleiotropic signaling moleculeAp4A then binds Hint1 to promote activation of MITF-targetgene transcription. Earlier work showed that Hint1 can also bind andhydrolyze Lys-AMP, possibly to constrain Ap4A production.Because Ap4A can result from condensation of other aa-AMP'swith ATP, the specificity of the Hint1 aa-AMP–hydrolysis activityis of interest. Here we show that Hint1 has broad specificity foradenylate hydrolysis, whose structural basis we revealed through high-resolutionstructures of Hint1 in complex with three different aa-AMP analogues.Hint1 recognizes only the common main chain of the aminoacyl moiety,and has no contact with the aa side chain. The α-amino groupis anchored by a cation-pi interaction with Trp123 at the C-terminusof Hint1. These results reveal the structural basis for the remarkableadenylate surveillance activity of Hint1, to potentially control Ap4A levels in the cell. [ABSTRACT FROM AUTHOR]

Mitomycins make up a class of natural molecules produced by Streptomyces with strong antibacterial and antitumor activities. MitM is a key postmitosane modification enzyme involved in mitomycin biosynthesis in Streptomyces caespitosus . This protein was previously suggested to catalyze the aziridinium methylation of mitomycin A and the mitomycin intermediate 9a-demethyl-mitomycin A as an N -methyltransferase. The structural basis for MitM to recognize cofactor S -adenosyl-l-methionine (SAM) and substrate mitomycin A is unknown. Here, we determined the crystal structures of apo -MitM and MitM-mitomycin A- S -adenosylhomocysteine (SAH) ternary complexes with resolutions of 2.23 and 2.80 Å, respectively. We found that MitM adopts a class I SAM-dependent methyltransferase fold and forms a homodimer in solution. Conformational changes in a series of residues involved in the formation of active pockets assist MitM in binding SAH and mitomycin A. In particular, the 28 ALGAASLGE 36 loop changes most significantly. When mitomycin A binds, the bending direction of this loop is reversed, changing the entrance of the active site from open to closed. This study provides structural insights into MitM's involvement in the postmitosane stage of mitomycin biosynthesis and provides a template for the engineering of methyltransferases.

Herein, nickel-aluminum-layered double hydroxide (NiAl-LDH) films were prepared by the hydrothermal method. Based on the photoinduced reduction ability and degradation of LDHs on heavy metal ions and organic compounds, NiAl-LDH films displayed favorable simultaneous removal performance. Benefiting from the electron traps of heavy metals reduced from solution, the coexisting metal ions improved the photocatalytic activity of NiAl-LDH films on methyl orange. The higher the Fermi level of coexisting metal ion was, the higher the photocatalytic degradation rate of methyl orange obtained. Meanwhile, the removal rates of heavy metal ions (Ag + , Pb 2+ , and Cu 2+ ) from wastewater were both enhanced and could reach 95%. NiAl-LDH films showed affinity toward Ag + . Furthermore, NiAl-LDH films are tightly coupled with the substrate, providing active sites and a simple method for the catalyst recovery. This study provides new insights into the simultaneous removal of heavy metal ions and organic pollutants using LDH films., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Aminoacyl-tRNA synthetases, the essential enzyme family for protein translation, are attractive targets for developing antibacterial, antifungal, and antiparasitic agents and for treating other human diseases. The antimalarial natural product cladosporin was discovered recently as a novel lysyl-tRNA synthetase (LysRS) specific inhibitor. Here, we report a thorough analysis of cladosporin derivatives using chemical synthesis, biophysical, and biochemical experiments. A series of isocoumarin derivatives with only one nonhydrogen atom/bond change per compound was synthesized. These changes include replacements of methyltetrahydropyran moiety by methylcyclohexane or cyclohexane, lactone by lactam, hydroxyl groups by methoxyl groups, and dismission of the chiral center at C3 with a Δ 3,4 double bond. We evaluated these compounds by thermal shift assays and enzymatic experiments and further studied their molecular recognition by the Plasmodium falciparum LysRS through total five high-resolution crystal structures. Our results showed that the methyltetrahydropyran moiety of cladosporin could be replaced by a more stable methylcyclohexane without reducing binding ability. Removing the methyl group from the methylcyclohexane moiety slightly decreased the interaction with LysRS. Besides, the replacement with a lactam group or a conjugated Δ 3,4 double bond within the scaffold could be two more options to optimize the compound. Lastly, the two phenolic hydroxyl groups were critical for the compounds to bind LysRS. The detailed analyses at atomic resolution in this study provide a foundation for the further development of new antibiotics from cladosporin derivatives.

Proton exchange membrane fuel cell (PEMFC) is one of the most promising green power sources, in which perfluorinated sulfonic acid ionomer-based membranes (e.g., Nafion) are widely used. However, the widespread application of PEMFCs is greatly limited by the sharp degradation in electrochemical properties of the proton exchange membranes under high temperature and low humidity conditions. In this work, the high-performance sulfonated carbon nanotubes/Nafion composite membranes (Su-CNTs/Nafion) for the PEMFCs were prepared and the mechanism of the microstructures on the macroscopic properties of membranes was intensively studied. Microstructure evolution in Nafion membranes during water uptake was investigated by positron annihilation lifetime spectroscopy, and results strongly showed that the Su-CNTs or CNTs in Nafion composite membranes significantly reinforced Nafion matrices, which influenced the development of ionic-water clusters in them. Proton conductivities in Su-CNTs/Nafion composite membranes were remarkably enhanced due to the mass formation of proton-conducting pathways (water channels) along the Su-CNTs. In particular, these pathways along Su-CNTs in Su-CNTs/Nafion membranes interconnected the isolated ionic-water clusters at low humidity and resulted in less tortuosity of the water channel network for proton transportation at high humidity. At a high temperature of 135 °C, Su-CNTs/Nafion membranes maintained high proton conductivity because the reinforcement of Su-CNTs on Nafion matrices reduced the evaporation of water molecules from membranes as well as the hydrophilic Su-CNTs were helpful for binding water molecules.

In this work, we report the growth and functional characterizations of multiferroic TbMnO3 thin films grown on Nb-doped SrTiO3 (001) substrates using pulsed laser deposition. By performing detailed magnetic and ferroelectric properties measurements, we demonstrate that the multiferroicity of spin origin known in the bulk crystals can be successfully transferred to TbMnO3 thin films. Meanwhile, anomalous magnetic transition and unusual magnetoelectric coupling related to Tb moments are observed, suggesting a modified magnetic configuration of Tb in the films as compared to the bulk counterpart. In addition, it is found that the magnetoelectric coupling enabled by Tb moments can even be seen far above the Tb spin ordering temperature, which provides a larger temperature range for the magnetoelectric control involving Tb moments.

Spinocerebellar ataxia type 10 (SCA10) is caused by a pentanucleotide repeat expansion of r(AUUCU) within intron 9 of the ATXN10 pre-mRNA. The RNA causes disease by a gain-of-function mechanism in which it inactivates proteins involved in RNA biogenesis. Spectroscopic studies showed that r(AUUCU) repeats form a hairpin structure; however, there were no high-resolution structural models prior to this work. Herein, we report the first crystal structure of model r(AUUCU) repeats refined to 2.8 Å and analysis of the structure via molecular dynamics simulations. The r(AUUCU) tracts adopt an overall A-form geometry in which 3 × 3 nucleotide (5')UCU(3')/(3')UCU(5') internal loops are closed by AU pairs. Helical parameters of the refined structure as well as the corresponding electron density map on the crystallographic model reflect dynamic features of the internal loop. The computational analyses captured dynamic motion of the loop closing pairs, which can form single-stranded conformations with relatively low energies. Overall, the results presented here suggest the possibility for r(AUUCU) repeats to form metastable A-from structures, which can rearrange into single-stranded conformations and attract proteins such as heterogeneous nuclear ribonucleoprotein K (hnRNP K). The information presented here may aid in the rational design of therapeutics targeting this RNA.

Protein arginine deiminases (PADs) are calcium-dependent histone-modifying enzymes whose activity is dysregulated in inflammatory diseases and cancer. PAD2 functions as an Estrogen Receptor (ER) coactivator in breast cancer cells via the citrullination of histone tail arginine residues at ER binding sites. Although an attractive therapeutic target, the mechanisms that regulate PAD2 activity are largely unknown, especially the detailed role of how calcium facilitates enzyme activation. To gain insights into these regulatory processes, we determined the first structures of PAD2 (27 in total), and through calcium-titrations by X-ray crystallography, determined the order of binding and affinity for the six calcium ions that bind and activate this enzyme. These structures also identified several PAD2 regulatory elements, including a calcium switch that controls proper positioning of the catalytic cysteine residue, and a novel active site shielding mechanism. Additional biochemical and mass-spectrometry-based hydrogen/deuterium exchange studies support these structural findings. The identification of multiple intermediate calcium-bound structures along the PAD2 activation pathway provides critical insights that will aid the development of allosteric inhibitors targeting the PADs.

An out-of-plane elastic vibration test method is developed to directly study the elastic stability of elastic Ti foil-supported porous carbon nanocomposite (CNC) counter electrode (CE) of dye sensitized solar cells (DSSCs). The stability of CE, estimated by that of power conversion efficiency (PCE) of the CE-based DSSC device, is studied from the views of CNC morphology, equivalent resistances, exchange current density and contact model of CE. The results suggest thinner thickness and bigger interbundling degree of CNC layer is beneficial to the total internal impedance value of CE, and then beneficial to the CE stability. With optimal CNC structure, even if the CE is springed 1000 times with max amplification about 10 mm, the PCE of CE-based DSSC can remain 80% of the initial value. The test method is interesting and the results may have a potential use for elastic stability study of general elastic devices.

Protein arginine deiminase activity (PAD) is increased in cancer, rheumatoid arthritis, and ulcerative colitis. Although the link between abnormal PAD activity and disease is clear, the relative contribution of the individual PADs to human disease is not known; there are 5 PAD isozymes in humans. Building on our previous development of F- and Cl-amidine as potent pan-PAD irreversible inhibitors, we describe herein a library approach that was used to identify PAD-selective inhibitors. Specifically, we describe the identification of Thr-Asp-F-amidine (TDFA) as a highly potent PAD4 inactivator that displays ≥15-fold selectivity for PAD4 versus PAD1 and ≥50-fold versus PADs 2 and 3. This compound is active in cells and can be used to inhibit PAD4 activity in cellulo. The structure of the PAD4·TDFA complex has also been solved, and the structure and mutagenesis data indicate that the enhanced potency is due to interactions between the side chains of Q346, R374, and R639. Finally, we converted TDFA into a PAD4-selective ABPP and demonstrated that this compound, biotin-TDFA, can be used to selectively isolate purified PAD4 in vitro. In total, TDFA and biotin-TDFA represent PAD4-selective chemical probes that can be used to study the physiological roles of this enzyme.

RNA internal loops often display a variety of conformations in solution. Herein, we visualize conformational heterogeneity in the context of the 5'CUG/3'GUC repeat motif present in the RNA that causes myotonic dystrophy type 1 (DM1). Specifically, two crystal structures of a model DM1 triplet repeating construct, 5'r[UUGGGC(CUG)(3)GUCC](2), refined to 2.20 and 1.52 Å resolution are disclosed. Here, differences in the orientation of the 5' dangling UU end between the two structures induce changes in the backbone groove width, which reveals that noncanonical 1 × 1 nucleotide UU internal loops can display an ensemble of pairing conformations. In the 2.20 Å structure, CUGa, the 5' UU forms a one hydrogen-bonded pair with a 5' UU of a neighboring helix in the unit cell to form a pseudoinfinite helix. The central 1 × 1 nucleotide UU internal loop has no hydrogen bonds, while the terminal 1 × 1 nucleotide UU internal loops each form a one-hydrogen bond pair. In the 1.52 Å structure, CUGb, the 5' UU dangling end is tucked into the major groove of the duplex. While the canonically paired bases show no change in base pairing, in CUGb the terminal 1 × 1 nucleotide UU internal loops now form two hydrogen-bonded pairs. Thus, the shift in the major groove induced by the 5' UU dangling end alters noncanonical base patterns. Collectively, these structures indicate that 1 × 1 nucleotide UU internal loops in DM1 may sample multiple conformations in vivo. This observation has implications for the recognition of this RNA, and other repeating transcripts, by protein and small molecule ligands.

TiO(2) nanocrystals with tunable bulk/surface defects were synthesized and characterized with TEM, XRD, BET, positron annihilation, and photocurrent measurements. The effect of defects on photocatalytic activity was studied. It was found for the first time that decreasing the relative concentration ratio of bulk defects to surface defects in TiO(2) nanocrystals could significantly improve the separation efficiency of photogenerated electrons and holes, thus significantly enhancing the photocatalytic efficiency.

Interface enhancement with carbon nanotubes (CNTs) provides a promising approach for improving shock strength and toughness of glass fiber reinforced plastic (GFRP) composites. The effects of incorporating flame-synthesized CNTs (F-CNTs) into GFRP were studied, including on hand lay-up preparation, microstructural characterization, mechanical properties, fracture morphologies, and theoretical calculation. The experimental results showed that: (1) the impact strength of the GFRP modified by F-CNTs increased by more than 15% over that of the GFRP modified by CNTs from chemical vapor deposition; and (2) with the F-CNT enhancement, no interfacial debonding was observed at the interface between the fiber and resin matrix on the GFRP fracture surface, which indicated strong adhesive strength between them. The theoretical calculation revealed that the intrinsic characteristics of the F-CNTs, including lower crystallinity with a large number of defects and chemical functional groups on the surface, promoted their surface activity and dispersibility at the interface, which improved the interfacial bond strength of GFRP.

Different assemblies of accessory proteins with clathrin are critical for transporting precisely various cargos between intracellular compartments. GGA proteins are adaptors for clathrin-mediated intracellular trafficking, connecting other accessory and cargo proteins to clathrin-coated vesicles. Both binding to the GAE domain of GGA protein yGGA2 in Saccharomyces cerevisia, Ent3 and Ent5 are involved in different trafficking pathways. Ent5 is ubiquitous and localized in a manner independent of yGGA2, and Ent3 functions preferentially through yGGA2. Not known are the sources of these differences. Here we show not all acidic-phenylalanine motifs in Ent3/5 are active for yGGA2_GAE domain binding. Two of the three acidic-phenylalanine motifs from Ent3 can bind to the yGGA2_GAE domain, while only one of the two motifs from Ent5 can bind. We also determined the crystal structure of the yGGA2_GAE domain at 1.8 A resolution. Structural docking and mutagenesis analysis shows inactive motifs in Ent3 and Ent5 repel yGGA2_GAE binding through disfavored residues at positions 1 and 3. These results suggest accessory proteins may fine-tune the GGA adaptor dependence by adjusting their non-acidic-phenylalanine residues, thus contributing to the distinct role of Ent3 and Ent5 in trafficking.

The photocatalytic activity of TiO(2) is enhanced mainly through heightening absorption of UV-vis light and improving the separation efficiency of photoinduced electrons and holes. The recent new theoretical research revealed that the TiO(2) codoped with Mo + C is considered to be an optimal doping system. On the basis of this theory, the Mo + C codoped TiO(2) powders were first experimentally synthesized by thermal oxidizing a mixture of TiC and MoO(3) powders in the air. The XRD patterns and the XPS survey spectrum showed that carbon (C) acted as a Ti-O-C band structure and molybdenum (Mo) existed as Mo(6+) in anatase TiO(2). The Mo+C codoped TiO(2) had a 32 nm red shift of the spectrum onset compared with pure anatase TiO(2), and its band gap was reduced from 3.20 to 2.97 eV. The photocurrent of the Mo + C codoped TiO(2) was about 4 times as high as that of pure anatase TiO(2), and its photocatalytic activity on decomposition of methylene blue was enhanced.

Through comparing the photocatalytic performance of microscale ZnO, nano ZnO, and Degussa P25 titania (P25), it was found that the microscale ZnO exhibited 2.6-35.7 times higher photocatalytic activity for the photodegradation of various dye pollutants than P25 under both UV-visible and visible irradiation and showed much better photostability than the nano ZnO. The photocatalysts were characterized with XRD, Raman, BET, DRUV-vis, adsorption of dye, photoelectrochemical measurement, and PL. The much higher photocataltyic activity of the microscale ZnO than P25 under UV-visible irradiation is attributed to the higher efficiency of generation, mobility, and separation of photoinduced electrons and holes. The much higher visible photocataltyic activity of the microscale ZnO than P25 is due to the higher photosensitization efficiency of electron transfer from an excited dye to the conduction band of the microscale ZnO than that of P25. The much better photostability of the microscale ZnO than the nano ZnO is due to its better crystallinity and lower defects. The photostability of the microscale ZnO is greatly improved by the surface modification of ZnO with a small amount of TiO(2). On the basis of the excellent photocatalytic performance of the microscale ZnO and TiO(2)-modified ZnO, a novel device of coupling photodegradation with light-to-electricity conversion was developed, which is a promising candidate for the photocatalytic removal of dye pollutants and a renewable energy source.