A new catalyst based on a nickel(II) complex of diiminodiphosphine for hydrogen evolution and oxidation

Based on that hydrogen energy is widely used in fuel cells, we focus our interests on the design and research of new complexes that catalyze the reaction in both directions, such as hydrogen evolution reactions (HERs) and hydrogen oxidation reactions (HORs). A highly efficient catalyst for both hydrogen evolution and oxidation, based on a nickel(II) complex, [Ni-en-P₂](ClO₄)₂, has been designed and provided by the reaction of Ni(ClO₄)₂ with N,N′-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (en-P₂) in our group. Its structure has been determined by X-ray diffraction. [Ni-en-P₂](ClO₄)₂ can electro-catalyze hydrogen evolution both from acetic acid and a neutral buffer (pH 7.0) with a turnover frequency (TOF) of 204 and 1327 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) under an overpotential (OP) of 914.6 mV and 836.6 mV, respectively. [Ni-en-P₂](ClO₄)₂ also can electro-catalyze hydrogen oxidation with a TOF of 111.7 s⁻¹ under an OP of 330 mV. The results can be attributed to that [Ni^II-en-P₂](ClO₄)₂ has three good reversible redox waves at 1.01 (Ni^III/II), −0.79 (Ni^II/I) and −1.38 V (Ni^I/0) versus Fc^+/0, respectively. We hope these findings can afford a new method for the design of electrocatalysts for both H₂ evolution and H₂ oxidation.     

钛基Ce掺杂SnO_2-RuO_2电极的制备及其对焦化废水的电解处理

采用溶胶-凝胶法制备了经稀土元素Ce掺杂改性的Ti/RuO_2-SnO_2-Ce电极,利用SEM、XRD、EDS等分析方法对电极表面的形貌、物相和涂层成分进行了表征,利用CV曲线、LSV曲线等检测手段对电极的电化学性能进行了测试。以Ti/RuO_2-SnO_2-Ce电极为阳极,钛板为阴极,构建电化学氧化反应装置,并采用其对焦化废水进行电解处理。结果表明,Ti/RuO_2-SnO_2电极经稀土Ce改性后极板表面活性位点数量明显增大,金属涂层的结晶化程度明显增强,电极的催化氧化活性显著提高。室温条件下,保持pH值为7.83,在电流密度为30mA/cm~2,电解时间为30min时,焦化废水经电解处理后COD去除率可达91.63%,TOC去除率可达66.22%,UV254值下降到0.921。     

铜基化合物的可见光催化研究进展

与传统贵金属光催化剂相比，铜基光催化剂具有价格低廉、绿色环保、反应条件温和、光催化活性可调节等优势，受到合成化学家们广泛关注。本文简述了铜基催化剂的光催化历史，回顾了近五年来铜基化合物在可见光催化领域的研究成果与进展，总结了铜基催化剂的独立光催化机理与协同光催化机理；简要阐述了铜催化剂在不同类型反应中的应用，重点讨论了铜(Ⅰ)催化剂在烯烃官能化、碳-碳偶联、碳-杂偶联、原位催化等反应中的应用研究，表明铜基化合物在光催化合成领域具有很大的应用潜力。对未来的研究工作进行了展望，指出拓展催化剂的反应适用性、探索催化剂的氧化还原能力、进一步开发催化剂在手性合成中的应用将是该领域的研究重点。     

7,8-Dihydro-8-oxoguanosine Lesions Inhibit the Theophylline Aptamer or Change Its Selectivity

Aptamers are attractive constructs due to their high affinity/selectivity towards a target. Here 7,8-dihydro-8-oxoguanosine (8-oxoG) has been used, due in part to its unique H-bonding capabilities (Watson–Crick or Hoogsteen), to expand the “RNA alphabet”. Its impact on the theophylline RNA aptamer was explored by modifying its binding pocket at positions G11, G25, or G26. Structural probing, with RNases A and T₁, showed that modification at G11 leads to a drastic structural change, whereas the G25-/G26-modified analogues exhibited cleavage patterns similar to that of the canonical construct. The recognition properties towards three xanthine derivatives were then explored through thermophoresis. Modifying the aptamer at position G11 led to binding inhibition. Modification at G25, however, changed the selectivity towards theobromine (K_d≈160 μm ), with a poor affinity for theophylline (K_d>1.5 mm ) being observed. Overall, 8-oxoG can have an impact on the structures of aptamers in a position-dependent manner, leading to altered target selectivity.     

A quarter century of wine pigment discovery

The red grape berry pigments, anthocyanins, were characterized in the early 20th century, but investigations of wine pigments were stymied during that era. The question of their identity was a major challenge for wine chemists. A number of techniques showed that the pigments were polymeric in nature. Some structures were postulated by mid-century based on reactions between anthocyanins and condensed tannin, and later postulated wine pigments were observed in model reactions. Some related compounds were then observed in wine. By the end of the 20th century, the ionization of non-volatiles for mass spectrometry opened the door to these compounds. In addition, a new class of compounds was observed, the pyranoanthocyanins, a product of fermentation and aging metabolites with anthocyanins. These compounds possess the pigment stability to SO₂ and pH change that is characteristic of aged red wine. Aging experiments show a dynamic situation with shifts in the population of pigment classes over time. The very large number of diverse pigments explains why it has been so difficult to answer the century-old question of the structure of wine pigments. Our current understanding is founded on the use of mass spectral analysis using electrospray and related ionization techniques over the last 25 years. Future progress will rely on more sophisticated analysis of this very complex mixture of substances. © 2019 Society of Chemical Industry     

Antioxidant Activity of Rambutan (Nephelium lappaceum L.) Peel Extract in Soybean Oil during Storage and Deep Frying

Rambutan (Nephelium lappaceum L.) peel (RBP) is discarded as the main by‐product during processing of the fruit. Increasing attention is now paid to the valorization of RBP for the recovery of valuable compounds. Geraniin, ellagic acid, quercetin, and rutin are the main phenolic compounds found in methanolic RBP extract. Extracted rambutan peel powder (ERPP) is used to evaluate the oxidative stability of soybean oil stored at 4 and 30 °C in the dark and light and deep fried with potatoes at 160 °C. Tert‐butylhydroquinone (100 µg g^?1 oil, TBHQ) serves as positive control. Oil supplemented with ERPP of 1000 µg gallic acid equivalents (GAE) g^?1 of oil shows positive effects on the retardation of the oxidation process during storage in comparison with oil without addition. During deep frying, either ERPP (1000 µg GAE g^?1) or TBHQ retards the lipid oxidation of oil. Levels of thiobarbituric acid reactive substances of potatoes fried in oil fortified with the extract and TBHQ (0.4–0.59 µg g^?1) are much lower than those without the extract (1.31 ± 0.10 µg g^?1) (p < 0.05). Therefore, RBP extract exhibits favorable antioxidant effects and can be used for effectively inhibiting lipid oxidation in oil during storage and deep frying. Practical Applications: An extract from rambutan fruit peel containing phenolic compounds, that is, geraniin, ellagic acid, rutin, and quercetin showed promising results to be used as potential antioxidants in soybean oil during deep frying. Both oxidation of the frying oil as well as the oxidation of the food product, that is, potatoes were inhibited. These results demonstrated that rambutan fruit peel extract can be used as a natural antioxidant in frying oil to replace synthetic antioxidants, that is, TBHQ.     

Investigation of flame spray synthesized La1-xSrxCoO3 perovskites with promotional catalytic performances on CO oxidation

To enhance the activity of catalysts for CO removal, the perovskite-type catalysts La_1-xSr_xCoO₃ (x = 0, 0.2, 0.4, 0.6, and 0.8) with different Sr²⁺ doping amount were synthesized by flame spray synthesis (FSS) method. The perovskite-type catalyst synthesized by FSS has a much larger specific surface area (SSA) than that prepared by other conventional methods. The SSA of catalyst increases with the increase of Sr²⁺ doping amount and the SSA of La_0.2Sr_0.8CoO₃ reaches 31.65 m²/g. Compared with other conventional methods, FSS method significantly improves the activity of catalyst and makes it close to the performances of catalysts with surface modification. The substitution of La³⁺ by Sr²⁺ promotes the generation of secondary phase Co₃O₄ and SrCO₃. The catalytic activity of La_1-xSr_xCoO₃ increases with the addition of Sr²⁺, which results from the increasing active sites and oxygen vacancies. Interestingly, La_0.4Sr_0.6CoO₃ performs the highest activity for CO oxidation and the CO conversion reaches 50% at 148.6 °C and 90% at 165.9 °C. The oxidation of CO over La_1-xSr_xCoO₃ catalyst may follow a combination of MvK and L-H mechanisms according to the experimental results of H₂-TPR. Moreover, the catalyst exhibits good catalytic activity in consecutive oxidation cycles. In consecutive oxidation experiments with La_0.4Sr_0.6CoO₃, the CO conversion reaches 50% at 168.8 °C and 90% at 197.8 °C in the eighth oxidation cycle. These results prove that FSS method can further improve the activity of catalysts and is suitable for the preparation of efficient catalysts.