Isomerization of surface functionalized SWCNTs and the critical influence on photoluminescence: static calculations and excited-state dynamics simulations.

Single-walled carbon nanotubes (SWCNTs) functionalized with sparse surface chemical groups are promising for a variety of optical applications such as quantum information and bio-imaging. However, the luminescence efficiencies and stability, two key aspects, undoubtedly govern their practical usage. Herein, we assess the surface migration of oxygen and triazine groups on as-modified SWCNT fragments by adopting transition state theory and explore the de-excitation of oxygen-functionalized SWCNT fragments by performing non-adiabatic excited-state dynamics simulations. According to the predicted moderate or even small reaction barriers, the migration of both oxygen and triazine groups is feasible from an sp3 defect configuration forming an energetically more stable sp2 configuration at moderate or even room temperatures. Such isomerization leads to drastically different light emission capabilities as indicated by the large or zero oscillator strengths. During the dynamics simulations, the lowest excited singlet (S1) state rapidly decays in energy within 20 fs and then fluctuates until the end, providing insights into the emission mechanism of SWCNTs. This study highlights the potential intrinsic limitations of surface-functionalized SWCNTs for luminescence applications.

Controllable Exfoliation of MOF-Derived Van Der Waals Superstructure into Ultrathin 2D B/N Co-Doped Porous Carbon Nanosheets: A Superior Catalyst for Ambient Ammonia Electrosynthesis.

The electrocatalytic nitrogen reduction reaction (NRR) to synthesize NH3 under ambient conditions is a promising alternative route to the conventional Haber-Bosch process, but it is still a great challenge to develop electrocatalysts' high Faraday efficiency and ammonia yield. Herein, a facile and efficient exfoliation strategy to synthesize ultrathin 2D boron and nitrogen co-doped porous carbon nanosheets (B/NC NS) via a metal-organic framework (MOF)-derived van der Waals superstructure, is reported. The results of experiments and theoretical calculations show that the doping of boron and nitrogen can modulate the electronic structure of the adjacent carbon atoms; which thus, promotes the competitive adsorption of nitrogen and reduces the energy required for ammonia synthesis. The B/NC NS exhibits excellent catalytic performance and stability in electrocatalytic NRR, with a yield rate of 153.4 µg·h-1 ·mg-1 cat and a Faraday efficiency of 33.1%, which is better than most of the reported NRR electrocatalysts. The ammonia yield of B/NC NS can maintain 92.7% of the initial NRR activity after 48 h stability test. The authors' controllable exfoliation strategy using MOF-derived van der Waals superstructure can provide a new insight for the synthesis of other 2D materials.

Co-Doped Ni3V2O8 Nanofibers Achieving d-d Orbital Coupling for Electrocatalytic Oxygen Reduction.

Efficient and robust non-platinum-group metal electrocatalysts for O2 reduction are a prerequisite for practical high-performance fuel cells and metal-air batteries. Herein, we reported an integrated principle of gradient electrospinning and controllable pyrolysis to fabricate various Co-doped Ni3V2O8 nanofibers with high oxygen reduction reaction (ORR) activity. The representative Co1.3Ni1.7V2O8 nanofibers showed outstanding ORR performance in an alkaline solution with a half-wave potential (E1/2) of 0.874 V vs RHE, along with high long-term stability. Furthermore, the introduction of Co could effectively restrain the growth of nanoparticles and change the electronic structure of Ni3V2O8. Control experiments and theoretical calculations demonstrated that upon Co-doping, the hybridization between the 3d orbital for both Co and Ni guaranteed the stable adsorption interaction with O2 over Ni and Co metal centers. Meanwhile, the weakened binding ability of Ni3V2O8 to OH* reduced the ORR free energy. Overall, the synergistic effect of Co and Ni metal cations essentially reflected the origin of ORR activity on the Co-doped Ni3V2O8 nanofibers. This work offers new insights and practical guidance for designing highly active ORR catalysts for electrochemical clean energy conversion and storage.

Amperometric hydrogen peroxide and glucose biosensor based on NiFe2/ordered mesoporous carbon nanocomposites.

Nanocomposites of NiFex embedded in ordered mesoporous carbon (OMC) (x = 0, 1, 2) were prepared by a wet impregnation and hydrogen reduction process and were used to construct electrochemical biosensors for the amperometric detection of hydrogen peroxide (H2O2) or glucose. The NiFe2/OMC nanocomposites were demonstrated to have a large surface area, suitable mesoporous channels, many edge-plane-like defective sites, and a good distribution of alloyed nanoparticles. The NiFe2/OMC and Nafion modified glass carbon electrode (GCE) exhibited excellent electrocatalytic activities toward the reduction of H2O2 as well. By utilizing it as a bioplatform, GOx (glucose oxidase) cross-linked with Nafion was immobilized on the surface of the electrode for the construction of an amperometric glucose biosensor. Our results indicated that the amperometric hydrogen peroxide biosensor (NiFe2/OMC + Nafion + GCE) showed good analytical performances in term of a high sensitivity of 4.29 µA mM(-1) cm(-2), wide linearity from 6.2 to 42,710 µM and a low detection limit of 0.24 µM at a signal-to-noise ratio of 3 (S/N = 3). This biosensor exhibited excellent selectivity, high stability and negligible interference for the detection of H2O2. In addition, the immobilized enzyme on NiFe2/OMC + Nafion + GCE, retaining its bioactivity, exhibited a reversible two-proton and two-electron transfer reaction, a fast heterogeneous electron transfer rate and an effective Michaelis-Menten constant (K) (3.18 mM). The GOx + NiFe2/OMC + Nafion + GCE could be used to detect glucose based on the oxidation of glucose catalyzed by GOx and exhibited a wide detection range of 48.6-12,500 µM with a high sensitivity of 6.9 µA mM(-1) cm(-2) and a low detection limit of 2.7 µM (S/N = 3). The enzymic biosensor maintained a high selectivity and stability features, and shows great promise for application in the detection of glucose.

Nitrogen doped TiO2-Cu(x)O core-shell mesoporous spherical hybrids for high-performance dye-sensitized solar cells.

We report on high-performance dye-sensitized solar cells (DSSCs) based on nitrogen doped anatase TiO2-CuxO core-shell mesoporous hybrids synthesized through a facile and controlled combined sol-gel and hydrothermal process in the presence of hexadecylamine as the structure-directing agent. The matching of band edges between CuxO and TiO2 to form a semiconductor heterojunction plays an important role in effective separation of light induced electrons and holes, providing a promising photoanode for DSSCs because of its wide absorption spectrum, high electron injection efficiency, and fast electron transference. DSSCs based on the mesoporous TiO2-CuxO core-shell hybrids show a high short-circuit current density of 9.60 mA cm(-2) and a conversion efficiency of 3.86% under one sun illumination. While DSSCs based on the N-doped mesoporous TiO2-CuxO hybrids exhibit the higher short-circuit current density of 13.24 mA cm(-2) and a conversion efficiency of 4.57% under one sun illumination. In comparison with un-doped TiO2-CuxO hybrids, the doping of nitrogen into the lattice of TiO2 can extend the light absorption in the ultraviolet range to the visible light region and effectively decrease the recombination rate of photo-generated electrons and holes. The presented N-doped mesoporous TiO2-CuxO hybrids as photoanodes could find potential applications for high performance DSSCs.

0D/1D CuWO4/Mn0.3Cd0.7S S-scheme heterojunctions for full-spectrum bifunctional photocatalytic degradation and hydrogen production.

Integrating photocatalytic oxidation for pollutant removal with hydrogen production via photocatalysis presents a promising approach for sustainable water purification and renewable energy generation, circumventing the sluggish multi-electron transfer inherent in photocatalytic water oxidation. This study introduces novel zero-/one-dimensional (0D/1D) CuWO4/Mn0.3Cd0.7S step-scheme (S-scheme) heterojunctions that exhibit exceptional bifunctional capabilities in photocatalytic degradation and hydrogen production under full-spectrum illumination. The degradation efficiency for tetracycline (TC) using 5 %-CuWO4/Mn0.3Cd0.7S reaches 94.3 % and 94.5 % within 60 min and 6 h, respectively, under ultraviolet-visible (UV-Vis) and near-infrared (NIR) light. Notably, these 0D/1D CuWO4/Mn0.3Cd0.7S S-scheme heterojunctions demonstrate superior hydrogen production, achieving rates of 12442.03 µL g-1h-1 and 2418.54 µL g-1h-1 under UV-Vis light and NIR light irradiation, respectively-these rates are 2.3 times and 55.2 times higher than that of Mn0.3Cd0.7S alone. This performance enhancement is attributed to the intrinsic dimensional effects, transitions of transition metal d-d orbitals, and S-scheme hole/electron (h+/e-) separation characteristics. Additionally, experimental results and density functional theory (DFT) calculations have clarified the modulation of electronic configurations, band alignment, and interfacial interactions via 0D/1D S-scheme heterojunction engineering. This study sheds light on the electron transfer mechanism within S-scheme heterojunction and enhances the effectiveness, economy, and sustainability of recalcitrant pollutant removal and hydrogen production.

Efficient wide-spectrum one-dimensional MWO4 (M = Mn, Co, and Cd) photocatalysts: Synthesis, characterization and density functional theory study.

Broadening the absorption region to near-infrared (NIR) light is critical for the photocatalysis due to the larger proportion and stronger penetration of NIR light in solar energy. In the present paper, one-dimensional (1D) MWO4 (M = Mn, Co, and Cd) materials synthesized by electrospinning technique, were studied by combining the density functional theory (DFT) with experiment results, which possessed the enhanced light absorption capability within the range of 200-2000 nm. It was proved that in the ultraviolet-visible (UV-Vis) region, the absorption bands of CoWO4 and MnWO4 samples were attributed to the metal-to-metal charge transfer mechanism, while the absorption of CdWO4 sample may be referable to the ligand-to-metal charge transfer mechanism. In the near-infrared (NIR) region, the absorption of CoWO4 and MnWO4 primarily originated from the d-d orbital transitions of Mn2+ and Co2+. The photocatalytic experimental results showed that the degradation rates for bisphenol A (BPA) over CoWO4, MnWO4, and CdWO4 photocatalysts under UV-Vis/NIR light irradiation for 140 min/12 h were 78.8 %/75.9 %, 23.8 %/21.3 %, 12.8 %/8.7 %, respectively. This research offers the novel insights into the precise construction of tungstate catalytic systems and contributes to the advancement of UV-Vis-NIR full spectrum photocatalytic technology, and lays a foundation for a cleaner and more environmental-friendly future.

Molecular cloning of vasa gene and the effects of LHRH-A on its expression in blue tilapia Oreochromis aureus.

The full length of vasa cDNA in blue tilapia Oreochromis aureus was cloned and sequenced using reverse transcription-polymerase chain reaction (RT-PCR) and rapid amplification of cDNA ends (RACE). Nucleotide sequence analysis revealed that the cDNA contained 2,143 bp and was consisted of a 48-bp 5' untranslated terminal region (5'-UTR), a 157-bp 3' untranslated terminal region (3'-UTR) and a 1,938-bp open reading frame (ORF) which encoded 645 amino acids. Homological protein analysis showed that vasa in O. aureus was highly conserved with Nile tilapia Oreochromis niloticus. Tissue distribution expression analysis indicated that vasa was specifically expressed in the gonads. Using in situ hybridization, we found that vasa was expressed in spermatogonia and spermatocytes rather than spermatids and sperm. In order to examine the influence of luteinizing hormone releasing hormone analog (LHRH-A) on vasa, the in vivo injections were performed different concentrations of LHRH-A. Our results showed that LHRH-A induced meiosis and down-regulated vasa mRNA expression. In summary, our results showed that vasa was specifically expressed in gonads and LHRH-A inhibited vasa expression in the testis. Our results also suggested that LHRH-A could regulate vasa gene expression in O. aureus testis.

Electrospun Mesoporous InVO4 /TiO2 Nanobelts with Enhanced Photocatalytic Properties.

In the present paper, mesoporous InVO4 /TiO2 nanobelts with diameter about 400 nm have been synthesized by elaborately designed electrospinning process. The microstructures of InVO4 /TiO2 nanobelts are characterized in detail, and their photoelectrocatalytic properties are comprehensively investigated by the photocatalytic degradation tests with tetracycline (TTC) and rhodamine B (RhB) waste water. Furthermore, the energy bandgap and density of states of orthorhombic InVO4 and anatase TiO2 are modeled and analyzed by density functional theory. Compared with single InVO4 nanobelts and TiO2 nanofibers, mesoporous InVO4 /TiO2 nanobelts possess the extraordinary photocatalytic efficiencies and exceptional cycle performances, which may be ascribed to the successful construction of heterostructures between InVO4 and TiO2 and unique one-dimensional belt structures.

Mo-doped SnO2 mesoporous hollow structured spheres as anode materials for high-performance lithium ion batteries.

We designed a facile infiltration route to synthesize mesoporous hollow structured Mo doped SnO2 using silica spheres as templates. It is observed that Mo is uniformly incorporated into SnO2 lattice in the form of Mo(6+). The as-prepared mesoporous Mo-doped SnO2 LIBs anodes exhibit a significantly improved electrochemical performance with good cycling stability, high specific capacity and high rate capability. The mesoporous hollow Mo-doped SnO2 sample with 14 at% Mo doping content displays a specific capacity of 801 mA h g(-1) after 60 cycles at a current density of 100 mA g(-1), about 1.66 times higher than that of the pure SnO2 hollow sample. In addition, even if the current density is as high as 1600 mA g(-1) after 60 cycles, it could still retain a stable specific capacity of 530 mA h g(-1), exhibiting an extraordinary rate capability. The greatly improved electrochemical performance of the Mo-doped mesoporous hollow SnO2 sample could be attributed to the following factors. The large surface area and hollow structure can significantly enhance structural integrity by acting as mechanical buffer, effectively alleviating the volume changes generated during the lithiation/delithiation process. The incorporation of Mo into the lattice of SnO2 improves charge transfer kinetics and results in a faster Li(+) diffusion rate during the charge-discharge process.

Identification and characterization of microRNAs in ovary and testis of Nile tilapia (Oreochromis niloticus) by using solexa sequencing technology.

MicroRNAs (miRNAs) are endogenous non-coding small RNAs which play important roles in the regulation of gene expression by cleaving or inhibiting the translation of target gene transcripts. Thereinto, some specific miRNAs show regulatory activities in gonad development via translational control. In order to further understand the role of miRNA-mediated posttranscriptional regulation in Nile tilapia (Oreochromis niloticus) ovary and testis, two small RNA libraries of Nile tilapia were sequenced by Solexa small RNA deep sequencing methods. A total of 9,731,431 and 8,880,497 raw reads, representing 5,407,800 and 4,396,281 unique sequences were obtained from the sexually mature ovaries and testes, respectively. After comparing the small RNA sequences with the Rfam database, 1,432,210 reads in ovaries and 984,146 reads in testes were matched to the genome sequence of Nile tilapia. Bioinformatic analysis identified 764 mature miRNA, 209 miRNA-5p and 202 miRNA-3p were found in the two libraries, of which 525 known miRNAs are both expressed in the ovary and testis of Nile tilapia. Comparison of expression profiles of the testis, miR-727, miR-129 and miR-29 families were highly expressed in tilapia ovary. Additionally, miR-132, miR-212, miR-33a and miR-135b families, showed significant higher expression in testis compared with that in ovary. Furthermore, the expression patterns of the miRNAs were analyzed in different developmental stages of gonad. The result showed different expression patterns were observed during development of testis and ovary. In addition, the identification and characterization of differentially expressed miRNAs in the ovaries and testis of Nile tilapia provides important information on the role of miRNA in the regulation of the ovarian and testicular development and function. This data will be helpful to facilitate studies on the regulation of miRNAs during teleosts reproduction.