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The zinc-ion hybrid capacitor (ZIHC) is an emerging energy storage device that has attracted intense interest for the inherent merits of relatively higher energy density and power density. Herein, an excellent ZIHC based on the Nb2CTx anode and CNTs@MnO2 cathode has been rationally designed and fabricated successfully in this work. MnO2 nanoflakes were grown on carbon nanotubes (CNTs) directly with a hydrothermal approach. Then, the CNTs@MnO2 nanocomposite acted as a cathode in a zinc-ion battery. Nb2CTx, a kind of new layered compound in the MXene family, demonstrates excellent ion storage capability. The large interlayer space dramatically improves zinc-ion accessibility. A ZIHC with a Nb2CTx anode and a CNTs@MnO2 cathode displays an energy density of 96.7 Wh kg–1 (with 183.2 W kg–1) and a power density of 1156.3 W kg–1 (with 61 Wh kg–1), a capacitance retention of about 88.7% after 10,000 cycles, and a Coulombic efficiency of more than 98.5% in the whole cycling process. This strategy of designing the ZIHC may provide a promising route to create novel energy storage devices. [ABSTRACT FROM AUTHOR]

Owing to its high electrical conductivity, unique layered structure, and strong hydrophilicity, two-dimensional nanomaterial titanium carbide (Ti3C2Tx) has attracted considerable attention as an electrode material for energy storage systems (EESs). However, the applications of Ti3C2Tx in EESs are severely limited by self-restacking and −F surface terminations, which are usually inevitable during the preparation of Ti3C2Tx.To improve the electrochemical performance of Ti3C2Tx, the present authors doped Ti3C2Tx with nitrogen, preparing N–Ti3C2Tx, via thermal decomposition of urea. The interlayer spacing increased from 1.17 nm in Ti3C2Tx to 1.33 nm in N–Ti3C2Tx and the −F surface termination was largely reduced. Benefiting from the synergistic effect of modified surface termination and expanded interlayer spacing, the prepared N–Ti3C2Tx electrode in 1 M H2SO4 delivers a high specific capacitance (390 F g–1) at a current density of 1 A g–1 (approximately twice that of pristine Ti3C2Tx). To demonstrate the effectiveness of the method in other EESs, the Zn2+-storage capacity of the N–Ti3C2Tx electrode was tested in 1 M ZnSO4. The electrode exhibited a capacitance of 252 F g–1 at 1 A g–1, exceeding that of the pristine Ti3C2Tx electrode (212 F g–1). Furthermore, the energy and power densities of the N–Ti3C2Tx // MnO2–CNT system reached 26 W h kg–1 and 950 W kg–1, respectively, much larger than those of the Ti3C2Tx // MnO2–CNT system (13 W h kg–1 and 550 W kg–1, respectively). The proposed strategy can facilely functionalize Ti3C2Tx for use in different high-performing EESs. [ABSTRACT FROM AUTHOR]

The development of nanocluster (NC)-based luminescent functional materials has gained tremendous attention recently owing to their unique optical properties. Herein, we studied the coassembly behavior of AuNCs modified using 6-propyl-2-thiouracil (PRT-AuNCs) with trimesic acid (TA). Microrods were formed through the coassembly, accompanied with enhanced photoluminescence emission. The intermolecular hydrogen bonding and π–π stacking between TA and PRT ligands were verified to be the main driving forces for the formation of ordered aggregates and consequently the improvement of the luminescence of PRT-AuNCs. Furthermore, inspired by the outstanding optical properties of the PRT-AuNCs/TA complex, we prepared a luminescent nanocomposite hydrogel through loading the PRT-AuNCs/TA complex into κ-carrageenan networks. The obtained hydrogel showed strong luminescence, high strength, and self-healing properties. Moreover, by doping blue emission quantum dots (QDs), a type of multicolor hydrogel was obtained. The different pH-responsive behaviors of QDs and PRT-AuNCs render the multicolor hydrogel a candidate with potential applications in information encryption. This study proposes a new method for the development of AuNC-based nanomaterials through coassembly and provides a perspective for the potential usage of AuNCs as smart luminescent devices. [ABSTRACT FROM AUTHOR]

Hybrid nonlinear plasmonic waveguides, characterized by a small mode area and large nonlinear susceptibility, present an intriguing and practical platform for the minimization of nonlinear photonic devices. Nevertheless, the intrinsic Ohmic loss associated with surface plasmon polaritons (SPPs) and modal dispersion imposes constraints on the effective interaction length and, consequently, the ultimate efficiency of nonlinear processes. In this study, we demonstrate an efficient second harmonic generation (SHG) within a hybrid plasmonic waveguide by leveraging SPP-like modes at the fundamental wave and photonic-like modes at the SHG under phase matching conditions. The presence of photonic-like modes significantly reduces the SHG losses, while the SPP-like modes improve the modal overlap, resulting in SHG conversion efficiency up to 8.5% W -1 cm -2 in a 55 μm-long waveguide. Our findings offer new avenues for the minimization of nonlinear photonic devices on a chip.

The heme-containing chlorite dismutases catalyze the rapid and efficient decomposition of chlorite (ClO 2 - ) to yield Cl - and O 2 , and the catalytic efficiency of chlorite dismutase from Dechloromonas aromatica ( Da Cld) in catalyzing the decomposition of bromite (BrO 2 - ) was dependent on pH, which was supposed to be caused by the conversion of active Cpd I to the inactive Cpd II by proton-coupled electron transfer (PCET) from the pocket Tyr118 to the propionate side chain of heme at high pH. However, the direct evidence of PCET and how the pH affects the efficiency of Da Cld, as well as whether Cpd II is really inactive, are still poorly understood. Here, on the basis of the high-resolution crystal structures, the computational models in both acidic (pH 5.0) and alkaline (pH 9.0) environments were constructed, and a series of quantum mechanical/molecular mechanical calculations were performed. On the basis of our calculation results, the O-Br bond cleavage of BrO 2 - always follows the homolytic mode to generate Cpd II rather than Cpd I. It is different from the O-O cleavage of O 2 /H 2 O 2 or peracetic acid catalyzed by the other heme-containing enzymes. Thus, in the subsequent O-O rebound reaction, it is the Fe(IV)═O in Cpd II that combines with the O-Br radical. Because the porphyrin ring in Cpd II does not bear an unpaired electron, the previously suggested PCET from Tyr118 to the propionate side chain of heme was not theoretically recognized in an alkaline environment. In addition, the O-O rebound step in an alkaline solution corresponds to an energy barrier that is larger than that in an acidic environment, which can well explain the pH dependence of the activity of Da Cld. In addition, the protonation state of the propionic acid side chains of heme and the surrounding hydrogen bond networks were calculated to have a significant impact on the barriers of the O-O rebound step, which is mainly achieved by affecting the reactivity of the Fe(IV)═O group in Cpd II. In an acidic environment, the relatively weaker coordination of the O2 atom to Fe leads to its higher reactivity toward the O-O rebound reaction. These observations may provide useful information for understanding the catalysis of chlorite dismutases.

Microbial degradation is a highly efficient and reliable approach for mitigating the contamination of sulfonylurea herbicides, such as chlorimuron-ethyl, in soil and water. In this study, we aimed to assess whether Kj-mhpC plays a pivotal role in the degradation of chlorimuron-ethyl. Kj -mhpC enzyme purified via prokaryotic expression exhibited the highest catalytic activity for chlorimuron-ethyl at 35 °C and pH 7. Bioinformatic analysis and three-dimensional homologous modeling of Kj-mhpC were conducted. Additionally, the presence of Mg + and Cu 2+ ions partially inhibited but Pb 2+ ions completely inhibited the enzymatic activity of Kj -mhpC. LC/MS revealed that Kj -mhpC hydrolyzes the ester bond of chlorimuron-ethyl, resulting in the formation of 2-(4-chloro-6-methoxypyrimidine-2-amidoformamidesulfonyl) benzoic acid. Furthermore, the point mutation of serine at position 67 (Ser67) confirmed that it is the key amino acid at the active site for degrading chlorimuron-ethyl. This study enhanced the understanding of how chlorimuron-ethyl is degraded by microorganisms and provided a reference for bioremediation of the environment polluted with chlorimuron-ethyl.

Quorum sensing inhibitors (QSIs) are a class of compounds that can reduce the pathogenicity of bacteria without affecting bacterial growth. In this study, we designed and synthesized four series of 4-fluorophenyl-5-methylene-2(5 H )-furanone derivatives and evaluated their QSI activities. Among them, compound 23e not only showed excellent inhibitory activity against various virulence factors but also significantly enhanced the inhibitory activity of antibiotics ciprofloxacin and clarithromycin against two strains of Pseudomonas aeruginosa in vitro . What is even more exciting is that it remarkably increased the antibacterial effect in vivo in combination with ciprofloxacin in the bacteremia model infected with P. aeruginosa PAO1. Moreover, 23e had little hemolytic activity to mouse erythrocytes. Further, the results of GFP reporter fluorescence strain inhibition and β-galactosidase activity inhibition experiments demonstrated that 23e simultaneously targeted the three quorum sensing systems in P. aeruginosa . As a result, compound 23e could be used as an effective QSI for further development against bacterial infections.

Ti 3 C 2 T x MXene is a member of the recently discovered two-dimensional early transition metal carbide and nitride family of MXenes with potential applications in energy storage and heterogeneous catalysis at elevated temperatures. Here, we apply a suite of in situ techniques to probe Ti 3 C 2 T x MXene's thermal evolutions, including in situ X-ray diffraction (XRD), in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and integrated thermogravimetry-differential scanning calorimetry-mass spectrometry (TG-DSC-MS). In light of this set of in situ investigations, we find heterogeneity in the layering of Ti 3 C 2 T x MXene revealed only at higher temperatures. Our findings present behavior up to 600 °C, particularly interlayer water and -OH surface end-capping groups. In one group of layers, their interlayer spacing shrinks as water deintercalates, but the other group of layers unexpectedly shows no change in the interlayer spacing. This is strong evidence that intercalants act as guest pillaring agents in the latter layering group, which stabilize these layers at higher temperatures while keeping the interlayer space accessible.

Aluminum hydroxide is an effective defluoridation adsorbent; however, the poor defluoridation performance limits its wide application. In this work, amorphous and crystalline AlOOH adsorbents are synthesized through hydrolysis of Al salts, and their defluoridation performances are evaluated in terms of adsorption capacity and rate, sensitivity to pH value, and water quality after defluoridation. The defluoridation performance of AlOOH is closely related to the hydrolysis pH value, but hardly to the type of Al salts. The adsorbent can remove >95% fluoride in the first 2 min and reach adsorption equilibrium within 2 h, and the maximum defluoridation capacity is 41.9 mg/g. Furthermore, the adsorbent exhibits an excellent defluoridation efficiency at a wide pH range of 4.5-10.5. After fluoride removal, the adsorbents prepared at pH values of 6 and 7 exhibit low residual Al concentration. The Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) results confirm that the fluoride removal mechanism is the ligand exchange between fluoride and hydroxyl groups. The excellent defluoridation capacity and low residual Al demonstrate that AlOOH is a potential adsorbent for fluoride separation from water., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Low-temperature anaerobic methane conversion to methanol (MTM) using copper ion-exchanged mordenite (Cu-MOR) as the catalyst and water as the sole source of oxygen is promising for sustainable utilization of methane. Integrating in situ calorimetric, spectroscopic, and structural methodologies, we report a systematic study on energetics of water-cationic species-framework guest-host interactions as a function of water loading for several mordenites relevant to low-temperature MTM. Notably, the near-zero coverage hydration enthalpy on Cu-MOR is -133.1 ± 6.0 kJ/mol water, which is related to Cu-MOR regeneration using water as oxidant. The copper oxo sites are thermally stable up to 915 °C and remain chemically intact as an oxygen source after complete hydration and dehydration. This study underscores the importance of manipulating the oxidation state and coordination chemistry of transition metal guest species in zeolites by fine-tuning the partial pressure of water as a strategy for rational design, synthesis, and modification of catalysts.

Defining the energetic landscape of pseudocapacitive materials such as transition metal layered double hydroxides (LDHs) upon redox-site enrichment is essential to harnessing their power for effective energy storage. Here, coupling acid solution calorimetry, in situ XRD, and in situ DRIFTS, we demonstrate that as the Ni/Al ratio increases, both as-made (hydrated) and dehydrated NiAl-LDH samples are less stable as evidenced by their enthalpies of formation. Moreover, the higher specific capacity at an intermediate Ni/Al ratio of 3 is enabled by effective water-LDH interactions, which energetically stabilize the excessive near-surface Ni redox sites, solvate intercalated carbonate ions, and fill the expanded vdW gap, paying for the "energetic cost" of being "redox-site-rich". Thus, from a thermodynamic perspective, engineering molecule/solid-LDH interactions on the nanoscale with confined guest species other than water, which energetically impose stronger stabilization, may help us to achieve their specific capacitance potential.

We report on the fabrication of large-area all-carbon capacitors (ACCs) composed of multilayer stacks of carbon nanomembranes as dielectrics sandwiched between two carbon-based conducting electrodes. Carbon nanomembranes (CNMs) are prepared from aromatic self-assembled monolayers of phenylthiol homologues via electron irradiation. Two types of carbon-based electrode materials, (1) trilayer graphene made by chemical vapor deposition and mechanical stacking and (2) pyrolyzed graphitic carbon made by pyrolysis of cross-linked aromatic molecules, have been employed for this study. The capacitor area is defined by the width of electrode ribbons, and the separation between two electrodes is tuned by the number of CNM layers. Working ACCs with an area of up to 1200 μm 2 were successfully fabricated by a combination of bottom-up molecular self-assembly and top-down lithographic approaches. Then ACCs were characterized by Raman spectroscopy, helium ion microscopy, and impedance spectroscopy. A dielectric constant of 3.5 and an average capacitance density of 0.3 μF/cm 2 were derived from the obtained capacitances. A dielectric strength of 3.2 MV/cm was determined for CNMs embedded in graphene electrodes with the interfacial capacitance being taken into account. These results show the potential of carbon nanomembranes to be used as dielectric components in next-generation environment-friendly carbon-based energy storage devices.

The provision of clean water is a global challenge, and membrane filtration is a key technology to address it. Conventional filtration membranes are constrained by a trade-off between permeance and selectivity. Recently, some nanostructured membranes demonstrated the ability to overcome this limitation by utilizing well-defined carbon nanoconduits that allow a coordinated passage of water molecules. The fabrication of these materials is still very challenging, but their performance inspires research toward nanofabricated membranes. This study reports on molecularly thin membranes with sub-nanometer channels that combine high water selectivity with an exceptionally high permeance. Carbon nanomembranes (CNMs) of ∼1.2 nm thickness are fabricated from terphenylthiol (TPT) monolayers. Scanning probe microscopy and transport measurements reveal that TPT CNMs consist of a dense network of sub-nanometer channels that efficiently block the passage of most gases and liquids. However, water passes through with an extremely high permeance of ∼1.1 × 10 -4 mol·m -2 ·s -1 ·Pa -1 , as does helium, but with a ∼ 2500 times lower flux. Assuming all channels in a TPT CNM are active in mass transport, we find a single-channel permeation of ∼66 water molecules·s -1 ·Pa -1 . This suggests that water molecules translocate fast and cooperatively through the sub-nanometer channels, similar to carbon nanotubes and membrane proteins (aquaporins). CNMs are thus scalable two-dimensional sieves that can be utilized toward energy-efficient water purification.

Surface-enhanced Raman scattering spectroscopy (SERS) was employed to investigate the formation of self-assembled monolayers (SAMs) of biphenylthiol, 4'-nitro-1,1'-biphenyl-4-thiol, and p-terphenylthiol on Au surfaces and their structural transformations into carbon nanomembranes (CNMs) induced by electron irradiation. The high sensitivity of SERS allows us to identify two types of Raman scattering in electron-irradiated SAMs: (1) Raman-active sites exhibit similar bands as those of pristine SAMs in the fingerprint spectral region, but with indications of an amorphization process and (2) Raman-inactive sites show almost no Raman-scattering signals, except a very weak and broad D band, indicating a lack of structural order but for the presence of graphitic domains. Statistical analysis showed that the ratio of the number of Raman-active sites to the total number of measurement sites decreases exponentially with increasing the electron irradiation dose. The maximum degree of cross-linking ranged from 97 to 99% for the three SAMs. Proof-of-concept experiments were conducted to demonstrate potential applications of Raman-inactive CNMs as a supporting membrane for Raman analysis.

Opioid peptides are neuromodulators that bind to opioid receptors and reduce pain sensitivity. Endomorphins are among the most active endogenous opioid peptides, and they have good affinity and selectivity toward the μ opioid receptor. However, their clinical usage is hindered by their inability to cross the blood-brain barrier and their poor in vivo activity after peripheral injection. In order to overcome these defects, we have designed and synthesized a series of novel endomorphin analogs with multiple site modifications. Radioligand binding, cAMP accumulation, and β-arrestin-2 recruitment assays were employed to determine the activity of synthesized endomorphin analogs toward opioid receptors. The blood-brain barrier permeability and antinociceptive effect of these analogs were determined in several rodent models of acute and persistent pain. In addition, the side effects of the analogs were examined. The radioligand binding assay and functional activity examination indicated that the MEL-N16 series of compounds were more active agonists against μ opioid receptor than were the parent peptides. Notably, the analogs displayed biased downstream signaling toward G-protein pathways over β-arrestin-2 recruitment. The analogs showed highly potent antinociceptive effects in the tested nociceptive models. In comparison with endomorphins, the synthesized analogs were better able to penetrate the blood-brain barrier and exerted their pain regulatory activity in the central nervous system after peripheral injection. These analogs also have lower tendency to cause side effects than morphine does at similar or equal antinociceptive doses. The MEL-N16 compounds have highly potent and efficacious analgesic effects in various pain models with a favorable side effect profile.

A free-standing binder-free 3D Ni@NiO nanowire membrane is fabricated by a simple filtration method followed by thermal annealing. With an appropriate annealing temperature, the functional nanowires can keep their rough and echinate surface, and the conductive network composed of welded nickel nanowire cores is well-preserved without isolation (0.53 Ω/sq). The unique 3D multigrade mesporous structure not only accelerates the intercalation and deintercalation velocity of electrolyte ions but also provides numerous electroactive sites for the Faraday reaction. As a result, the supercapacitor electrode can preserve a capacitance retention of 96.1% (36.9 F/cm(3)) with a high discharge current density, indicating its wonderful rate capability. The fabricated membrane electrode exhibits high volumetric capacitance, stable cycling life, and remarkable retention of the capacitance at high rate, energy, and power density, making it a promising candidate for application in portable electronic products.

Freestanding carbon nanomembranes (CNMs) with a thickness between 0.6 and 1.7 nm were prepared from self-assembled monolayers (SAMs) of diverse polyaromatic precursors via low-energy electron-induced cross-linking. The mechanical properties of CNMs were investigated using AFM bulge test, where a pressure difference was applied to the membrane and the resulting deflection was measured by atomic force microscopy. We found a correlation between the rigidity of the precursor molecules and the macroscopic mechanical stiffness of CNMs. While CNMs from rigid and condensed precursors like naphthalene and pyrene thiols prove to exhibit higher Young's moduli of 15-19 GPa, CNMs from nonfused oligophenyls possess lower Young's moduli of ~10 GPa. For CNMs from less densely packed SAMs, the presence of defects and nanopores plays an important role in determining their mechanical properties. The finite element method (FEM) was applied to examine the deformation profiles and simulate the pressure-deflection relationships.

All-solid-state flexible supercapacitors based on a carbon/MnO(2) (C/M) core-shell fiber structure were fabricated with high electrochemical performance such as high rate capability with a scan rate up to 20 V s(-1), high volume capacitance of 2.5 F cm(-3), and an energy density of 2.2 × 10(-4) Wh cm(-3). By integrating with a triboelectric generator, supercapacitors could be charged and power commercial electronic devices, such as a liquid crystal display or a light-emitting-diode, demonstrating feasibility as an efficient storage component and self-powered micro/nanosystems.