ZSM-5分子筛上正碳离子发生D、F和G型β键断裂反应的探索研究

在C—C键断裂反应中,普遍认为：由于不同结构的正碳离子存在稳定性差异,导致A、B、C型β键断裂反应较容易发生,而D、E型β键断裂反应在常规条件下几乎不可能发生。针对正碳离子裂化反应机理中乙烯选择性差的问题,深入分析现有实验设计方法的局限性,重新设计实验方法并反复进行了实验研究。结果表明：在特定的催化条件下,能量上非常不利的D型和笔者自定义的F、G型正碳离子β键断裂反应可以在C—C键断裂反应中被有效促进并有助于提高乙烯选择性。这一发现,不仅丰富了正碳离子有机化学反应的内涵,也为乙烯高效生产提供崭新的开发思路。     

New isolate of Trichoderma viride strain for enhanced cellulolytic enzyme complex production

A new Trichoderma viride stain was isolated from Singapore soil samples. Its mutants were developed by using ethyl methyl sulfonate (EMS) treatment and UV-irradiation followed by a semi-quantitative plate clearing assay on phosphoric-acid-swollen cellulose plates. Mutant EU2-77 proved to be the most promising extracellular cellulase producer among 20 mutants in a screening program performed in shake flask fermentation after plate screening. Soluble protein content, filter paper cellulase (FPase) activity, β-glucosidase activity and endoglucanase (CMCase) activity of the fermentation broths of the mutant strain were increased to 1.67, 2.49, 2.16, and 2.61 folds, respectively, compared with the wild strain. This enzyme complex produced by mutant EU2-77 contained FPase (2.19 IU/ml), CMCase (16.46 IU/ml), β-glucosidase (4.04 IU/ml), xylanase (42.37 IU/ml), and β-xylosidase (0.12 IU/ml). The soluble protein concentration in the enzyme complex was 1.69 mg/ml. The hydrolytic capacities of fermentation supernatants of T. reesei Rut-C30, the wild strain T. viride NP13a and mutant T. viride EU2-77 were compared with the commercial enzymes on the hydrolysis of waste newspaper. The crude enzymes prepared by T. viride EU2-77 showed much higher hydrolysis performance than that from the commercial strain Rut-C30 and demonstrated much comparable hydrolytic performances with the commercial enzyme mixtures. T. viride mutant EU2-77 produced high levels of extracellular cellulases as well as β-glucosidase, rendering the supplementation of β-glucosidase unnecessary in waste newspaper hydrolysis.     

Dual effect of β-cyclodextrin (β-CD) on the inhibition of apple polyphenol oxidase by 4-hexylresorcinol (HR) and methyl jasmonate (MJ)

Inhibition of red delicious apple polyphenol oxidase (PPO) by three non-related antibrowning agents has been studied at different substrate concentrations. The main apple polyphenol, cholorogenic acid (CA), has been used as a substrate. The three agents (β-cyclodextrin [β-CD], 4-hexylresorcinol [HR] and methyl jasmonate [MJ]) showed an inhibitory effect at every substrate concentration tested. From the inhibition constant (K_i) values, it was concluded that the inhibitors’ strength decreased in the order HR > β-CD > MJ. A combination of β-CD-HR had a synergic effect, which was not observed for the combination of β-CD-MJ. A competitive-type inhibition was obtained for HR with a K_i = 0.26 mM. β-CD and MJ behaved as mixed-type inhibitors, although more than one inhibitory mechanism is discussed for both agents.     

Simultaneous HPLC quantification of total cholesterol,tocopherols and β-carotene in Barrosã-PDO veal

A simple, rapid and sensitive procedure for the simultaneous determination of total cholesterol, tocopherols and β-carotene in meat is described. The method involves a direct saponification of the meat, a single n-hexane extraction and the analysis of the extracted compounds by normal-phase HPLC, using fluorescence (tocopherols) and UV–Vis photodiode array (cholesterol and β-carotene) detections in tandem. Rates of recovery of spiked meat samples were 93% for cholesterol, 83–86% for (α-, β- and -γ) tocopherols and 89% for β-carotene. Repeatabilities were high (CV < 6%) for all determined compounds, except for δ-tocopherol. This tocopherol, which is not usually present in meat, showed a much lower recovery percentage (73%) and repeatability (12.8%). This methodology was applied for the quantification of total cholesterol, tocopherols and β-carotene in three muscles (longissimus thoracis, longissimus lumborum and semitendinosus) of the Portuguese traditional Barrosã-PDO veal, obtained from autochthonous calves fed extensively during summer (with the least abundant green pastures) and slaughtered in early autumn (October). Barrosã-PDO veal showed median contents of total cholesterol (0.50–0.56 mg/g) and, depending on the analysed muscle, moderate to high contents of α-tocopherol (3.3–3.9 μg/g) and β-carotene (0.07–0.09 μg/g), suggesting an high sensorial and hygienic quality.     

Effect of sodium addition on the preparation of hydroxyapatites and biphasic ceramics

HAP and biphasic ceramics of two different HAP and β-TCP proportions with substituted sodium were prepared through an aqueous precipitation method. The prepared powders were characterized by XRD, thermal analysis, FT-IR and elemental analysis. Sodium was found to incorporate into the apatite structure without showing any significant change in the phase behaviour of the resultant apatites. The substitution of sodium in the calcium deficient apatites tends to form a biphasic mixture of HAP and β-TCP, while the effect of calcination beyond 700 °C and the resultant mixtures were dependent on the initial Ca/P ratios of the precursors. The calculated lattice parameter values for sodium substituted apatites have shown a marginal increase in c-axis values thereby leading to the enlargement of the hexagonal cell volume with respect to the pure HAP prepared under the same experimental conditions. Powders obtained from the present results were stable up to 1200 °C.     

改性β环糊精絮凝剂的制备及性能研究

以环氧氯丙烷（EPI）为交联剂,在碱性介质中合成了β-环糊精（-βCD）水溶性交联聚合物,并以其为基体,以硝酸铈铵（CAN）为引发剂,在弱酸性条件下,合成出了新型的水溶性交联-βCD接枝聚丙烯酰胺（PAM）的共聚物絮凝剂（WCDP）.对产物的红外光谱分析（FTIR）表明WCDP的合成是成功的.研究了WCDP的制备条件（交联剂用量、引发剂用量、温度、时间等）对吸附有机污染物和除浊性能的影响,结果表明：在最佳合成条件下,WCDP能同时去除水中的浊度和小分子有机污染物,并能形成絮体从水中分离.以高岭土和对硝基苯酚（p-NP）为研究对象,WCDP对浊度和p-NP的去除率分别为96.7%和60.6%.     

Electrochemical micromachining using a solid electrochemical reaction at the metal/β″-Al2O3 microcontact

A simple solid state technique for electrochemical micromachining of metal substrates using a metal ion conductor (Na-β″-Al₂O₃) was proposed. The fundamental solid electrochemical cell consists of a (anode) metal substrate (M = Ag, Cu, Zn, and Pb)/pyramidal Na-β″-Al₂O₃/Ag (cathode) system, where the contact diameter between M/Na-β″-Al₂O₃ was extremely small, on the order of a few micrometer. Under an applied electric field, the metal substrate was electrochemically oxidized to metal ions (Mⁿ⁺) at the M/Na-β″-Al₂O₃ microcontact. These Mⁿ⁺ ions migrated into the Na-β″-Al₂O₃. As a result of continuous electrolysis, the metal substrate was locally consumed at the microcontact, and thus solid state electrochemical micromachining was accomplished. As expected, the machining size or depth depended on the electrolysis conditions (current, operating time) and the apex configuration of pyramidal Na-β″-Al₂O₃. Moreover, the scanning of the Na-β″-Al₂O₃ pyramid during electrolysis produced a fine patterned metal substrate. In the present paper, solid state electrochemical micromachining was performed for several metal substrates, and its advantages and disadvantages vis-a-vis the conventional electrochemical micromachining method are discussed in detail.     

Electrochemical investigation of uranium β-diketonates for all-uranium redox flow battery

The redox flow battery using uranium as the negative and the positive active materials in polar aprotic solvents was proposed. In order to establish the guiding principle for the uranium compounds as the active materials, the investigation of uranium β-diketonate complexes was conducted on (i) the solubility of active materials, (ii) the electrode reaction of U(VI) and U(IV) β-diketonate complexes and (iii) the estimation of the open circuit voltage of the battery. The solubilities of higher than 0.8 mol dm⁻³ of U(VI) complexes and higher than 0.4 mol dm⁻³ of a U(IV) complex were obtained in the solvents. The electrode reactions of U(pta)₄, UO₂(dpm)₂, UO₂(fod)₂ and UO₂(pta)₂ were first studied and the redox potentials of uranium β-diketonates were thermodynamically discussed. The open circuit voltage is estimated more than 1 V by using Hacac or Hdpm. The larger open circuit voltage is expected when a ligand with the larger basicity is used.     

四氯化锡催化合成β-萘甲醚

四氯化锡催化下,β 萘酚与无水甲醇反应合成β 萘甲醚,考察了甲醇用量、催化剂用量、反应时间等对产率的影响。当β 萘酚取1.8g,甲醇1.5mL,SnCl4·5H2O取0.33g时,80℃反应10h,β 萘甲醚产率可达75.3%。     

β-取代卟啉及卟啉锰对氧化破坏的稳定性

在假一级条件下,以亚碘酰苯为氧化剂,通过测定β-未取代的四苯基卟啉(TPP),以及不同β-取代的β-Cl8TPP、β-Br8TPP、β-Br4TPP、β-NO2TPP、β-(CH3)8TPP及其金属锰配合物的氧化破坏反应的表观动力学常数,获得了卟啉配体的稳定性顺序为TPP>β-(CH3)8TPP>β-Br8TPP>β-Cl8TPP>β-Br4TPP>β-NO2TPP,β位位阻越大相应的卟啉配体越稳定,并由此推导PhIO由β位进攻卟啉配体。β-取代锰卟啉的稳定性顺序为:Mn(β-Cl8TPP)Cl>Mn(β-Br8TPP)Cl>Mn(β-Br4TPP)Cl>Mn(β-NO2TPP)Cl>Mn(TPP)Cl>Mn[β-(CH3)8TPP]Cl,并与在催化氧化环己烷反应中的稳定性一致,β位吸电子作用越大相应的锰卟啉越稳定,并推导由氧化能力更强的高价金属-氧中间体以位阻较小的面对面方式进攻β-取代锰卟啉。