Revealing the Intrinsic Restructuring of Bi2O3 Nanoparticles into Bi Nanosheets during Electrochemical CO2 Reduction.

Bismuth is a catalyst material that selectively produces formate during the electrochemical reduction of CO2. While different synthesis strategies have been employed to create electrocatalysts with better performance, the restructuring of bismuth precatalysts during the reaction has also been previously reported. The mechanism behind the change has, however, remained unclear. Here, we show that Bi2O3 nanoparticles supported on Vulcan carbon intrinsically transform into stellated nanosheet aggregates upon exposure to an electrolyte. Liquid cell transmission electron microscopy observations first revealed the gradual restructuring of the nanoparticles into nanosheets in the presence of 0.1 M KHCO3 without an applied potential. Our experiments also associated the restructuring with solubility of bismuth in the electrolyte. While the consequent agglomerates were stable under moderate negative potentials (-0.3 VRHE), they dissolved over time at larger negative potentials (-0.4 and -0.5 VRHE). Operando Raman spectra collected during the reaction showed that under an applied potential, the oxide particles reduced to metallic bismuth, thereby confirming the metal as the working phase for producing formate. These results inform us about the working morphology of these electrocatalysts and their formation and degradation mechanisms.

Enhancing the electrocatalytic performance of SnX2 (X = S and Se) monolayers for CO2 reduction to HCOOH via transition metal atom adsorption: a theoretical investigation.

Exploring highly efficient, stable, and low-cost electrocatalysts for CO2 reduction reaction (CRR) can not only mitigate greenhouse gas emission but also store renewable energy. Herein, CO2 electroreduction to HCOOH on the surface of SnX2 (X = S and Se) monolayer-supported non-noble metal atoms (Fe, Co and Ni) was systematically investigated using first-principles calculations. Our results show that Fe, Co and Ni adsorbed on the surface of SnX2 (X = S and Se) monolayers can effectively enhance their electrocatalytic activity for CO2 reduction to HCOOH with low limiting potentials due to the decreasing energy barrier of *OOCH. Moreover, the lower free energy of the *OOCH intermediate on the surface of TM/SnX2 (X = S and Se) monolayers verifies that the electroreduction of CO2 to HCOOH prefers to proceed along the path: CO2 → *OOCH → *HCOOH → HCOOH. Interestingly, SnX2 (X = S and Se) monolayer-supported Co and Ni atoms prefer the HCOOH product with low CRR overpotentials of 0.03/0.01 V and 0.13/0.05 V, respectively, showing remarkable catalytic performance. This work reveals an efficient strategy to enhance the electrocatalytic performance of SnX2 (X = S and Se) monolayers for CO2 reduction to HCOOH, which could provide a way to design and develop new CRR catalysts experimentally in future.

Spatially and Chemically Resolved Visualization of Fe Incorporation into NiO Octahedra during the Oxygen Evolution Reaction.

The activity of Ni (hydr)oxides for the electrochemical evolution of oxygen (OER), a key component of the overall water splitting reaction, is known to be greatly enhanced by the incorporation of Fe. However, a complete understanding of the role of cationic Fe species and the nature of the catalyst surface under reaction conditions remains unclear. Here, using a combination of electrochemical cell and conventional transmission electron microscopy, we show how the surface of NiO electrocatalysts, with initially well-defined surface facets, restructures under applied potential and forms an active NiFe layered double (oxy)hydroxide (NiFe-LDH) when Fe3+ ions are present in the electrolyte. Continued OER under these conditions, however, leads to the creation of additional FeOx aggregates. Electrochemically, the NiFe-LDH formation correlates with a lower onset potential toward the OER, whereas the formation of the FeOx aggregates is accompanied by a gradual decrease in the OER activity. Complementary insight into the catalyst near-surface composition, structure, and chemical state is further extracted using X-ray photoelectron spectroscopy, operando Raman spectroscopy, and operando X-ray absorption spectroscopy together with measurements of Fe uptake by the electrocatalysts using time-resolved inductively coupled plasma mass spectrometry. Notably, we identified that the catalytic deactivation under stationary conditions is linked to the degradation of in situ-created NiFe-LDH. These insights exemplify the complexity of the active state formation and show how its structural and morphological evolution under different applied potentials can be directly linked to the catalyst activation and degradation.

Depositional patterns constrained by slope topography changes on seamounts.

Slope topography is known to control the spatial distribution of deposits on intraplate seamounts; however, relatively little is known about how slope topography changes constrain those depositional patterns. In this study, we analyse data on four lithotypes found on seamount slopes, including colloidal chemical deposits comprising mainly cobalt-rich crusts, and examine the relationships between the spatial distribution of these lithotypes and current slope topography. We use these relationships to discuss depositional patterns constrained by slope topography changes. Some depositional units in drill core samples are interpreted to have resulted from past topographic changes that created the current slope topography. Two or more types of deposits that accumulated at the same location implies that the slope topography changed over time and that the depositional patterns on seamount slopes are constrained by changes in slope topography.

Modulating the Electronic, Optical, and Transport Properties of CdTe and ZnTe Nanostructures with Organic Molecules: A Theoretical Investigation.

In this paper, we systematically investigated the electronic, optical, and transport properties of CdTe and ZnTe nanostructures before and after adsorption with benzyl viologen (BV) and tetrafluoro-tetracyanoquinodimethane (F4-TCNQ) organic molecules based on the first principles calculation. First, the band gaps of CdTe and ZnTe nanostructures obviously decrease after BV and F4-TCNQ adsorptions. Interestingly, the electronic property calculation shows that BV and F4-TCNQ can donate/accept electrons to/from the surface of CdTe and ZnTe nanostructures, leading to an effective n-/p-type doping, respectively. Second, the optical absorption in a broad spectral range (from visible to near-infrared) of CdTe and ZnTe is significantly improved by adsorption of BV and F4-TCNQ molecules, offering great opportunities for the use of CdTe and ZnTe nanostructures in renewable energy fields. Lastly, the electrical transfer characteristics on CdTe and ZnTe nanostructure-based field-effect transistors clearly showed that the conduction of the nanostructures can be rationally tuned into n- and p-type conductivity with BV and F4-TCNQ adsorptions, respectively. Our work clearly demonstrates that the electronic, optical, and transport properties of CdTe and ZnTe nanostructures are effectively modulated by adsorption of BV and F4-TCNQ, which can be used to construct high-performance electronic and optoelectronic devices.

Characterization of a Cu2+, SDS, alcohol and glucose tolerant GH1 ß-glucosidase from Bacillus sp. CGMCC 1.16541.

A ß-glucosidase gene (bsbgl1a) from Bacillus sp. CGMCC 1.16541 was expressed in Escherichia coli BL21 and subsequently characterized. The amino acid sequence shared 83.64% identity with ß-glucosidase (WP_066390903.1) from Fictibacillus phosphorivorans. The recombinant ß-glucosidase (BsBgl1A) had a molecular weight of 52.2 kDa and could hydrolyze cellobiose, cellotriose, cellotetrose, p-nitrophenyl-ß-D-glucopyranoside (pNPG), and p-nitrophenyl-ß-D-xylopyranoside (pNPX). Optimal activity for BsBgl1A was recorded at 45 °C with a pH between 5.6 and 7.6, and 100% of its activity was maintained after a 24 h incubation between pH 4 and 9. Kinetic characterization revealed an enzymatic turnover (Kcat) of 616 ± 2 s-1 (with cellobiose) and 3.5 ± 0.1 s-1 (with p-nitrophenyl-ß-D-glucopyranoside). Interestingly, the recombinant enzyme showed cupric ion (Cu2+), sodium dodecyl sulfate (SDS) and alcohol tolerance at 10 mM for Cu2+ and 10% for both SDS and alcohol. Additionally, BsBgl1A had high tolerance for glucose (Ki = 2095 mM), which is an extremely desirable feature for industrial applications. Following the addition of BsBgl1A (0.05 mg/ml) to a commercial cellulase reaction system, glucose yields from sugarcane bagasse increased 100% after 1 day at 45 °C. This work identifies a Cu2+, SDS, alcohol, and glucose tolerant GH1 ß-glucosidase with potential applications in the hydrolysis of cellulose for the bioenergy industry.

A Reverse Strategy to Restore the Moisture-deteriorated Luminescence Properties and Improve the Humidity Resistance of Mn4+ -doped Fluoride Phosphors.

Fluoride phosphors as red components for warm white LEDs have attracted a tremendous amount of research attention. But these phosphors are extremely sensitive to moisture, which seriously limits their practical industrial applications. To tackle this problem, unlike all the straightforward preventive strategies, a reverse strategy "Good comes from bad" was successfully developed to treat the degraded K2 SiF6 : Mn4+ (D-KSFM) phosphor in the present study, which not only completely restores the luminescence properties, but also significantly enhances the moisture resistance at the same time. After treatment with an oxalic acid solution as restoration modifier, the emission intensity of the D-KSFM phosphor can be restored to 103.7% of the original K2 SiF6 : Mn4+ red phosphor (O-KSFM), and the moisture resistance is remarkably improved. The restored K2 SiF6 : Mn4+ (R-KSFM) maintains approximately 62.3% of its initial relative emission intensity after immersing in deionized water for 300 min, while the reference commercial K2 SiF6 : Mn4+ with a protective coating (C-KSFM) is only 33.2%. As a proof of general applicability, this strategy was also conducted to K2 TiF6 : Mn4+ phosphor, which is less moisture-stable than K2 SiF6 : Mn4+ . The luminescence intensity of the degraded K2 TiF6 : Mn4+ (D-KTFM) phosphor can be restored to 162.6% of original level of the K2 TiF6 : Mn4+ synthesized through a cation exchange approach without any treatment (O-KTFM). The emission intensity of the restored K2 TiF6 : Mn4+ (R-KTFM) phosphor retains 62.8% of its initial emission intensity after soaking in deionized water for 300 min. Finally, the R-KSFM phosphors were packaged into white light-emitting diodes with blue InGaN chips and Y3 Al5 O12 : Ce3+ yellow phosphors. The WLEDs display excellent color rendition with higher color rendering index, lower color temperature (WLED-II: Ra =83.6, R9 =57.3, 3743 K, ηl =199.68 lm/W; WLED-III: Ra =90.4, R9 =94.2, 2892 K, ηl =183.3 1 m/W). The above results show that the reverse strategy can be applied in those phosphor materials with poor moisture resistance to restore luminescence properties and improve moisture resistance without excessively care about the deterioration during the production, storage and transportation.

A narrow-band ultra-bright green phosphor for LED-based applications.

A novel Sr2MgB2O6 (SMBO) green-emitting phosphor co-doped with Ce3+-Tb3+ was synthesized at 950 °C via solid-state reactions, and the ultra-narrow-band green emission of Tb3+ was significantly enhanced almost 20 times via energy transfer from Ce3+ to Tb3+. It was found to have a broad excitation band (250 to 400 nm), and the full width at half-maximum (FWHM) of the dominant green emission band around 544 nm was only about 10 nm. The electronic band gap of the SMBO matrix was calculated by density functional theory (DFT) to be 4.60 eV, and this was well verified by the diffuse reflection spectra results. Furthermore, the composition-optimized phosphor SMBO:0.05Ce3+,0.05Tb3+ exhibits excellent thermal quenching resistance (75.3% intensity at 423 K) and relatively high external quantum efficiency (EQE = 48.92%). Finally, two white light-emitting diode (WLED) packages were fabricated via combining a 365 nm n-UV chip, the optimal sample and commercial blue and red phosphors to assess the application potential of the phosphors. The test results indicate that the obtained WLEDs-1 fabricated with K2SiF6:Mn4+ has an outstanding color rendering index (Ra = 85.7) and Commission Internationale de L'Eclairage (CIE) coordinates (0.3242, 0.3334). Meanwhile, the color gamut can reach 87% of the National Television Standards Committee (NTSC) CIE 1931 color gamut. WLEDs-2 fabricated with red emitting CaAlSiN3:Eu2+ produced warm white light with color coordinates of (0.3792, 0.3810), a high color rendering index of 82.3, and a low correlated color temperature of 4065 K. These results reveal the broad prospects of this phosphor for LED-based applications.

Cs2MnF6 Red Phosphor with Ultrahigh Absorption Efficiency.

To improve absorption efficiency (AE) and subsequently improve external quantum efficiency (EQE) remains one of the significant challenges for Mn4+-doped red-emitting fluoride phosphors. In this study, we propose to use Mn4+ as a part of matrix to enhance the AE of fluoride phosphors. Red-emission phosphors Cs2MnF6, Cs2MnF6:Sc3+, and Cs2MnF6:Si4+ were synthesized successfully by a coprecipitation method. The Rietveld refinement of X-ray diffraction reveals that this red phosphor exhibits a cubic structure in Fm3̅m space group. Owing to Mn4+ being a part of matrix, this kind of red phosphor possesses an extremely high AE, which can be promoted to 88%. The doping of Sc3+ and Si4+ ions into Cs2MnF6 can effectively increase the luminescence intensity to 253 and 232%, respectively, relative to that of Cs2MnF6. The relative emission intensity of Cs2MnF6:5%Si4+ red phosphor preserves about 115% when temperature rises to 175 °C. By employing Cs2MnF6:5%Si4+ as a red-emitting component, high-performance LED-1 with Ra = 86.2, R9 = 82.1 and CCT = 3297 K, and LED-2 with an ultrawide color gamut (NTSC value of 122.3% and rec. 2020 value of 91.3%) are obtained. This work may provide a new idea to explore a new type of fluoride phosphor with high EQE for high-performance white-light-emitting diodes.

Calibration of camera intrinsic parameters based on the properties of the polar of circular points.

Three-dimensional stratified reconstruction from images requires acquisition of circular points. This study proposes a new algorithm for calibrating camera intrinsic parameters using the properties of the polar of circular points (PCPs). Because the PCPs are asymptotic, which are self-conjugate diameters of the circle, the obtained PCPs can determine the image of the circular points and a group of orthogonal vanishing points in the image plane. On this basis, the camera parameters can be calibrated. The results of the simulation experiment and the data of the real experiment prove that the proposed method is effective and feasible.

Acetaminophen aggravates fat accumulation in NAFLD by inhibiting autophagy via the AMPK/mTOR pathway.

Non-alcoholic fatty liver disease (NAFLD) is the most common chronic liver disease which affects millions of people worldwide. Acetaminophen (APAP) overdose is the leading cause of acute liver failure. In this study, APAP (50, 100, 200 mg/kg) were employed on mice fed with a high-fat diet, and APAP (2, 4, 8 mM) were cultured with L02 cells in the presence of alcohol and oleic acid. APAP treatment significantly aggravated hepatic lipid accumulation, increased the serum levels of triglyceride (TG), alanine aminotransferase (ALT) and aspartate aminotransferase (AST), and increased hepatic lipid accumulation in H&E and Oil red O staining results. Transmission electron microscopy (TEM) found fewer number of autophagosomes in APAP (100 mg/kg) treated group. Immunohistochemistry analysis showed the intensity of hepatic mTOR was increased and AMPK was decreased in 200 mg/kg APAP treated group. Western blot analysis showed APAP treatment decreased the levels of LC3-Ⅱ, Beclin1 and AMPK, while increased the levels of mTOR and SREBP-1c, respectively. In vitro study showed APAP treatment obviously increased TG activities in cell supernatant, and Oil red O staining had the same results. Western blot analysis demonstrated APAP treatment decreased the levels of LC3-Ⅱ, Beclin1 and AMPK, increased the levels of mTOR and SREBP-1c, but rapamycin treatment significantly reversed these effects of APAP. In conclusion, therapeutic dosages of APAP aggravates fat accumulation in NAFLD, the potential mechanism might be involved in inhibiting autophagy associated with the AMPK/mTOR pathway, and patients with NAFLD should use a lower dose of APAP.

Acidic Mesoporous Zeolite ZSM-5 Supported Cu Catalyst with Good Catalytic Performance in the Hydroxysulfurization of Styrenes with Disulfides.

Development of highly active heterogeneous catalysts is an effective strategy for modern organic synthesis chemistry. In this work, acidic mesoporous zeolite ZSM-5 (HZSM-5-M), acidic-free mesoporous zeolite TS-1 (TS-1-M), and basic ETS-10 zeolite supported metal Cu catalysts were prepared to investigate their catalytic performances in the hydroxysulfurization of styrenes with diaryl disulfides. The effect of pore size and acidities of the supports, as well as the Cu species electronic properties of the catalysts on reaction activity were investigated. The results show that Cu⁺ and Cu2+ binded on HZSM-5-M show the highest activity and product selectivity for the desired ß-hydroxysulfides compounds.

Resveratrol Ameliorates Alcoholic Fatty Liver by Inducing Autophagy.

Alcoholic fatty liver (AFL) is early stage of alcoholic liver disease, which can progress to steatohepatitis, fibrosis, and cirrhosis if alcohol consumption is continued. The pathogenesis of AFL is associated with excessive lipid accumulation in hepatocytes. Resveratrol (RES), a dietary polyphenol found in red wines and grapes, has been shown to have a hepatoprotective effect. Autophagy is a crucial physiological process in cellular catabolism that involves the regulation of lipid droplets. Autophagy maintains a balance between protein synthesis, degradation and self-recycling. In the present study, we evaluated the protective effects of RES (10[Formula: see text]mg/kg, 30[Formula: see text]mg/kg, 100[Formula: see text]mg/kg) on AFL mice fed with an ethanol Lieber-DeCarli liquid diet, and HepG2 cells in the presence of oleic acid and alcohol to investigate whether resveratrol could induce autophagy to attenuate lipid accumulation. The results showed that RES (30[Formula: see text]mg/kg and 100[Formula: see text]mg/kg) treatment significantly attenuated hepatic steatosis and lowered the activities of serum alanine aminotransferase (ALT), aspartate aminotransferase (AST), triglyceride (TG), low density lipoprotein cholesterol (LDL-C). H&E staining showed that RES reduced hepatic lipid accumulation. Transmission electron microscopy (TEM) images showed that RES treatment increased the number of autophagosomes and promoted the formation of autophagy. Western blot analysis showed that RES treatment increased the levels of microtubule-associated protein light chain3- II (LC3-II) and Beclin1, decreased expression of p62 protein. In addition, in vitro studies also demonstrated that RES led to the formation of acidic vesicular organelles (AVOs), however, 3-Methyladenine (3-MA), a specific inhibitor of autophagy, obviously inhibited the above effects of RES. In conclusion, RES has protective effects on alcoholic hepatic steatosis, and the potential mechanism might be involved in inducing autophagy.

Tantalum compounds as heterogeneous catalysts for saccharide dehydration to 5-hydroxymethylfurfural.

A new solid acid, based on tantalum hydroxide, was used to catalyze saccharide dehydration into 5-hydroxymethylfurfural (HMF) with high catalytic activity and excellent stability in a water-2-butanol biphasic system. Furthermore, good results were also obtained from Jerusalem artichoke juice with the catalyst under the same conditions.

Conversion of biomass into 5-hydroxymethylfurfural using solid acid catalyst.

5-Hydroxymethylfurfural (HMF) was produced from monosaccharide (fructose and glucose), polysaccharide (inulin) and the Jerusalem artichoke juice by a simple one-pot reaction including hydrolysis and dehydration using solid acid under mild condition. Hydrated niobium pentoxide (Nb(2)O(5)·nH(2)O(2)) after pretreatment showed high catalytic activities for dehydration of mono- and polysaccharide to HMF at 433 K in water-2-butanol (2:3 v/v) biphasic system, giving high HMF yield of 89% and 54% from fructose and inulin, respectively. The HMF yield was up to 74% and 65% when inulin and Jerusalem artichoke juice were hydrolyzed by exoinulinase. The solid acid made the process environment-friendly and energy-efficient to convert carbohydrates into bio-fuels and platform chemicals.

Characterization of monoclonal antibodies for lead-chelate complexes: applications in antibody-based assays.

Monoclonal antibodies against lead were generated by immunizing BALB/c mice with lead conjugated to keyhole limpet hemocyanin (KLH) via a bifunctional chelator, S-2-(4-aminobenzyl)diethylenetriamine pentaacetic acid (DTPA). Stable hybridoma cell lines were produced by fusion of murine splenocytes and SP2/0 myeloma cells. One of the hybridomas generated from this fusion (4/7) synthesized and secreted an antibody that bound tightly to Pb2+-DTPA complexes but not to metal-free DTPA. The performance for a competitive inhibition enzyme-linked immunosorbent assay (ELISA) incorporating this antibody was assessed for its sensitivity to changes in pH, ionic strength, and blocking reagents. The cross-reactivities in this ELISA were less than 3% for Fe3+, Cd2+, Hg2+, and Cu2+ and less than 0.3% for Cr3+, Mn2+, Mg2+, In3+, Ag1+, Ni2+, Co2+, Zn2+, Ca2+, Cu1+, and Hg1+. The IC50 value achieved for lead was 2.72 +/- 0.034 microM, showing the detection range of 0.092-87.2 microM and the lowest detection limit of 0.056 +/- 0.005 microM. Recoveries from the analyte-fortified tap water and ultrapure water were in the range of 80-114% . These results indicate that the ELISA could be a convenient analytical tool for monitoring lead residues in drinking water.