Improved Urea Oxidation Performance via Interface Electron Redistributions of the NiFe(OH)x/MnO2/NF p-p Heterojunction.

The development of highly efficient urea oxidation reaction (UOR) electrocatalysts is the key to simultaneously achieving green hydrogen production and the treatment of urea-containing wastewater. Ni-based electrocatalysts are expected to replace precious metal catalysts for UOR because of their high activity and low cost. However, the construction of Ni-based electrocatalysts that can synergistically enhance UOR still needs further in-depth study. In this study, highly active electrocatalysts of NiFe(OH)x/MnO2 p-p heterostructures are constructed on nickel foam (NF) by electrodeposition (NiFe(OH)x/MnO2/NF), illustrating the effect of electronic structure changes at heterogeneous interfaces on UOR and revealing the catalytic mechanism of UOR. The NiFe(OH)x/MnO2/NF only needs 1.364 V (vs Reversible Hydrogen Electrode, RHE) to reach 10 mA cm-2 for UOR. Structural characterizations and theoretical calculations indicate that energy gap leads to directed charge transfer and redistribution at the heterojunction interface, forming electron-rich (MnO2) and electron-poor (NiFe(OH)x) regions. This enhances the catalyst's adsorption of urea and reaction intermediates, reduces thermodynamic barriers during the UOR process, promotes the formation of Ni3+ phases at lower potentials, and thus improves UOR performance. This work provides a new idea for the development of Ni-based high-efficiency UOR electrocatalysts.

Ethanol Electrooxidation on an Island-Like Nanoporous Gold/Palladium Electrocatalyst in Alkaline Media: Electrocatalytic Properties and an In Situ Surface-Enhanced Raman Spectroscopy Study.

The design of electrocatalysts with high activity and the understanding of the reaction mechanism for the ethanol oxidation reaction (EOR) are pivotal for commercializing direct ethanol fuel cells (DEFCs). Herein, island-like nanoporous gold/palladium (INPG/Pd) is designed as a highly efficient EOR electrocatalyst. For a better understanding of the reaction mechanism, in situ surface-enhanced Raman spectroscopy (SERS) in conjunction with H-D isotope replacement is used to investigate the dissociation and oxidation of CH3CH2OH on the INPG/Pd electrode, with a focus on identifying significant intermediate species in the reaction process. The results show that INPG/Pd has a higher electrocatalytic performance than INPG and indium-tin oxide (ITO) glass/palladium (Pd) due to the synergistic effect of NPG and Pd. INPG/Pd-10 shows the highest specific activity, the strongest charge-transfer ability, and relatively good stability. INPG/Pd presents better SERS sensitivity than ITO glass/Pd because of the plasma enhancement effect of nanoporous Au. The in situ Raman spectral results suggest that the oxidation of ethanol proceeds via a dual-pathway (C1 and C2) reaction mechanism. Dehydrogenation of ethanol can form acetaldehyde (CH3CHO) at -0.4 V. Meanwhile, the adsorbed acetaldehyde is oxidized to acetate from approximately -0.4 V, with the potential moving positively, which is the so-called C2 pathway. Alternatively, in the C1 pathway, CH3CHO and CH3CH2OH decomposed to intermediate species (adsorbed CO) on the INPG/Pd electrode due to C-C bond breaking at potentials of approximately -0.2 V. Subsequently, the CO species is oxidized to CO2 at more positive potentials.

Bismuth impregnated biochar for efficient uranium removal from solution: Adsorption behavior and interfacial mechanism.

In this work, Bi2O3 doped horse manure-derived biochar was obtained by carbonizing the H2O2-modified horse manure loaded with bismuth nitrate under nitrogen atmosphere at 500 °C. The results showed that there was a sharp response between the as-prepared bismuth impregnated biochar and uranium(VI) species in solution, which resulted in a short equilibrium time (<80 min), a fast adsorption rate (about 5.0 mg/(g·min)), a high removal efficiency (93.9%) and a large adsorption capacity (516.5 mg/g) (T = 298 K, pH = 4, Ci = 10 mg/L and m/V = 0.1 g/L). Besides, the removal behavior of the bismuth impregnated biochar for uranium(VI) did not depend on the interfering ions and ion strength, except Al3+, Ca2+, CO32- and PO43-. These results indicated that the modified biochar might possess the potential of remediating the actual uranium(VI)-containing wastewater. Moreover, the interaction mechanism between Bi2O3 doped biochar and uranium(VI) species was further explored. The results demonstrated that the enrichment of uranium(VI) on the surface of the as-prepared biochar was controlled by various factors, such as surface complexation, ion exchange, electrostatic attraction, precipitation and reduction, which facilitated the adsorption of uranium(VI) on the bismuth impregnated biochar.

The synthesis of a novel titanium oxide aerogel with highly enhanced removal of uranium and evaluation of the adsorption mechanism.

A TiO2 aerogel with a high removal percentage and adsorption capacity was manufactured via template synthesis. Subsequently, the as-prepared TiO2 aerogel was characterized by various techniques and applied as an adsorbent for the removal of U(vi). The results revealed that the U(vi) adsorption was very rapid and reached apparent equilibrium within 100 min. The maximum removal percentage was 97.1%, which was calculated using the pseudo-second-order kinetic model (T = 298 K, t = 180 min, pH = 5, m/V = 0.1 g L-1 and C0 = 10 mg g-1). The Langmuir isotherm model was used to determine the maximum adsorption capacity and it achieved 638.0 mg g-1 (T = 298 K, pH = 5 and m/V = 0.1 g L-1). In addition, the removal of U(vi) on the TiO2 aerogel was relatively good in acidic solution and the removal behavior was independent of the influence of ionic strength. The removal percentage of the as-prepared TiO2 aerogel was higher than 90% after five cycles. Due to these excellent properties such as easy recovery, fast adsorption kinetics, high adsorption capacity and high removal percentage, the TiO2 aerogel might become an extremely employable adsorbent for the extraction of U(vi) in seawater.

Toward the Limitation of Dealloying: Full Spectrum Responsive Ultralow Density Nanoporous Gold for Plasmonic Photocatalytic SERS.

Plasmon-mediated chemical reaction has a great potential to create self-cleaning surface-enhanced Raman scattering (SERS) substrates. However, few works have been reported to promote this goal. Here, we report ultralow density nanoporous gold (ULDNPG) that possesses an impressive full spectrum responsive characteristic with a reflectivity lower than 5% in the waveband of 300-900 nm. ULDNPG was fabricated by a sandwich dealloying strategy from ultradilute Au-Ag solid solutions with the Au content as low as 1-5 at.%. The prepared ULDNPG presents excellent SERS properties, including high sensitivity, high uniformity, and reproducibility. The full spectrum responsive characteristic of ULDNPG leads to an obvious plasmonic photocatalytic activity. The short lifetime of the SP-excited hot carriers causes a restricted self-cleaning SERS property and a strong photothermal effect for ULDNPG structures.

Association between the rs3733846 in the flanking region of miR-143/145 and risk of cervical squamous cell carcinoma.

Aim: To investigate the effect of rs3733846 in the flanking region of miR-143/145 on susceptibility to cervical squamous cell carcinoma (CSCC). Materials & methods: We collected venous blood samples from 242 CSCC patients and 250 healthy controls. The rs3733846 polymorphism was genotyped by SnaPshot and Sanger sequencing. The expression of miR-143/145 in CSCC tissues was detected by quantitative real-time PCR. Results: The rs3733846 AG genotype was associated with a decreased risk of CSCC in genetic model (AGvs.AA: adjusted odds ratio [OR]: 0.44; 95% CI: 0.30-0.66; p < 0.001). Patients with the rs3733846 AG/GG genotypes had a reduced risk of developing poorly differential status (OR: 0.57; 95% CI: 0.33-0.98; p < 0.04) and lymph node metastasis (OR: 0.49; 95% CI: 0.26-0.92; p < 0.03). Conclusion: The rs3733846 in the flanking region of miR-143/145 was related to the susceptibility of CSCC.

[Study on effect of total flavonoids from Scutellaria amoena on experimental arrhythmia].

OBJECTIVE: To observe the effect of total flavonoids from Scutellaria amoena on the experimental arrhythmia. METHOD: Experimental animals anesthetized with 10% chloral hydrate were evenly randomized into control group, positive control group, and low-dose, middle-dose and high-dose total flavonoids groups. The experimental arrhythmia ouabain-induced in guinea pigs and barium chloride or calcium chloride-induced in rats were observed and detected respectively. The result was converted into cumulative dosage of ouabain, in guinea pig model. In rat model, the duration of arrhythmia were detected. RESULT: hold dosage of ventricular premature heat (VP) and ventricular fibrillation( VF) ouabain-induced in guinea pigs was markedly elevated, and the duration of ventricular tachycardia (VT) barium chloride-induced and VF calcium chloride-induced in rats was postponed by total flavonoids from S. amoena. CONCLUSION: Total flavonoids from S. amoena has obvious protective effect on drug-induced arrhythmia.

A genetic variant rs13293512 in the promoter of let-7 is associated with an increased risk of breast cancer in Chinese women.

Growing evidence has demonstrated that single-nucleotide polymorphisms (SNPs) in the promoter of miRNA may influence individuals' susceptibility to human diseases. We examined two SNPs rs10877887 and rs13293512 in the promoters of let-7 family to determine if the two SNPs were related to the occurrence of breast cancer (BC). Genotyping of the two SNPs was performed by PCR and restriction fragment length polymorphism analysis or TaqMan assay in 301 BC patients and 310 age matched controls. We found a higher frequency of rs13293512 CC genotype and rs13293512 C allele amongst BC patients (CC vs TT: adjusted odds ratio (OR) = 1.78; 95% CI: 1.14-2.80; P=0.012; C vs T: adjusted OR = 1.33; 95% CI: 1.06-1.67; P=0.013). Stratification analysis showed that rs13293512 CC genotype was associated with an increased risk of BC in patients with negative estrogen receptor (adjusted OR = 2.39; 95% CI: 1.32-4.30; P=0.004), patients with negative progesterone receptor (adjusted OR = 1.92; 95% CI: 1.11-3.33; P=0.02), patients with T1-2 stage cancer (adjusted OR = 1.77; 95% CI: 1.07-2.93; P=0.03), and patients with N1-3 stage cancer (adjusted OR = 1.89; 95% CI: 1.13-3.17; P=0.015). These findings suggest that rs13293512 in the promoter of let-7a-1/let-7f-1/let-7d cluster may be a possible biomarker for the development of BC in Chinese women.

Island-like Nanoporous Gold: Smaller Island Generates Stronger Surface-Enhanced Raman Scattering.

The surface-enhanced Raman scattering properties of nanoporous gold prepared by the dealloying technique have been investigated for many years.The relatively low enhancement factor and the poor uniformity of existing conventional or advanced nanoporous gold structures are still the main factors that limit their wide application as Raman enhancement substrates. Here, we report island-like nanoporous gold (INPG) fabricated by simply controlling the composition of the dealloying precursor.This nanostructure can generate ∼10 times higher enhancement factor (above 107) with ∼4 times lower gold consumption than conventional nanoporous gold. The dimensions of the gold islands can be controlled by the composition of the precursor. The enhancement factor can therefore be controlled by the gold island dimensions, which suggests an effective approach to fabricate better Raman enhancement substrates. Furthermore, INPG exhibits excellent Raman enhancement uniformity and reproducibility with the relative standard deviations of only 2.5% and 6.5%, which originate from the extremely homogeneous structure of INPG at both the microscale and macroscale. The excellent surface-enhanced Raman scattering properties make INPG a potential surface-enhanced Raman scattering substrate.

Enhancement of electrochemical differentiation ability of nucleobases in phosphate buffer solution at pH 7.4.

The electrochemical behavior of nucleobases has been studied in 0.1 M phosphate buffer solution at pH 7.4, using a bare graphite electrode. Guanine and adenine produced well-defined oxidation peaks at about +0.63 and +0.91 V at 100 mV/s, respectively. Nucleobases exhibit an irreversible and hybrid-controlled electrochemical process, including adsorption and diffusion. The nucleobase oxidation peaks shift due to the selective interactions of nucleobases with each other. The oxidation peaks for three different pyrimidine bases, uracil, cytosine, and thymine, can be clearly identified at +1.26, +1.41, and +1.32 V, respectively. These differences in the electrochemical behavior among nucleobases can be attributed to their different chemical structures.

Glassy state lead tellurite nanobelts: synthesis and properties.

The lead tellurite nanobelts have been first synthesized in the composite molten salts (KNO3/LiNO3) method, which is cost-effective, one-step, easy to control, and performed at low-temperature and in ambient atmosphere. Scanning electron microscopy, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectrum, energy dispersive X-ray spectroscopy and FT-IR spectrum are used to characterize the structure, morphology, and composition of the samples. The results show that the as-synthesized products are amorphous and glassy nanobelts with widths of 200-300 nm and lengths up to tens of microns and the atomic ratio of Pb:Te:O is close to 1:1.5:4. Thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC) and investigations of the corresponding structure and morphology change confirm that the nanobelts have low glass transition temperature and thermal stability. Optical diffuse reflectance spectrum indicates that the lead tellurite nanobelts have two optical gaps at ca. 3.72 eV and 4.12 eV. Photoluminescence (PL) spectrum and fluorescence imaging of the products exhibit a blue emission (round 480 nm).