海洋真菌Gliocladium sp.中的甾体和酚类化合物

从山东乳山采集的海洋真菌Gliocladium sp.中分离得到2个甾体化合物和4个酚类化合物,经1H-NMR、13C-NMR和MS等现代波谱手段鉴定它们的结构分别为:麦角甾-5,7,22E-三烯-3β-醇(1)、23-甲基麦角甾-5,7,22E-三烯-3β-醇(2)、3-羟甲基苯酚(3)、4-甲基-1,2-二苯酚(4)、4-(2-羟乙基)苯酚(5)、2-羟基-6-甲基苯甲酸(6)。     

苯乙烯与苯酚反应的前线轨道理论分析

采用密度泛函理论的M062X方法和6-311G(d,p)基组,对苯乙烯与苯酚的反应进行了分子轨道理论计算。通过讨论反应过程中各分子的最高占据轨道(HOMO)和最低空轨道(LUMO),预测了化学反应的方向和相应的反应产物。经过前线轨道理论分析,得出苯乙烯与苯酚反应的关键步骤是形成苯乙烯基碳正离子,反应中H+起到催化作用;反应产物主要有4-(1-苯基乙基)苯酚、2-(1-苯基乙基)苯酚、2,4-双-(1-苯基乙基)苯酚分子、2,4,6-三-(1-苯基乙基)苯酚(SP-3)、1,3-二苯基丁烯和4-(1,2-二苯丙基)苯酚。     

苯乙烯与苯酚反应的前线轨道理论分析

采用密度泛函理论的M062X方法和6-311G(d,p)基组,对苯乙烯与苯酚的反应进行了分子轨道理论计算.通过讨论反应过程中各分子的最高占据轨道(HOMO)和最低空轨道(LUMO),预测了化学反应的方向和相应的反应产物.经过前线轨道理论分析,得出苯乙烯与苯酚反应的关键步骤是形成苯乙烯基碳正离子,反应中H+起到催化作用;反应产物主要有4-(1-苯基乙基)苯酚、2-(1-苯基乙基)苯酚、2,4-双-(1-苯基乙基)苯酚、2,4,6-三-(1-苯基乙基)苯酚(SP-3)、1,3-二苯基丁烯和4-(1,2-二苯丙基)苯酚.     

基于紫外吸收光谱的酚类衍生物含量检测研究

研究了水溶液条件下苯酚及其酚类衍生物的紫外吸收光谱。2位、3位和4位引入取代基可使酚类化合物的最大吸收波长λ_max发生红移,摩尔消光系数ε_max明显提高。不同取代位置对λ_max和ε_max的影响程度不同。与2位和3位相比,4位取代能使最大吸收波长λ_max发生较大红移,摩尔消光系数ε_max增加较大,这是因为4位取代基能与苯环形成更多共轭结构的缘故。对硝基酚的λ_max和ε_max的特性研究表明—NO₂是酚类化合物较好的助色基。由此,建立了快速测定酚类化合物含量的紫外分光光度法,并选择测定了ε_max>10 000的四种酚类化合物在土壤中的吸附率。结果显示,酚类化合物在质地粘重的土壤中吸附率较大;高浓度的无机盐溶液能够提高酚类化合物在土壤中的吸附率。     

One-pot reaction to synthesize superparamagnetic iron oxide nanoparticles by adding phenol as reducing agent and stabilizer

An improved thermal decomposition method was used to directly prepare water-soluble Fe₃O₄ magnetic nanoparticles (MNPs) with relatively higher quality via reductive decomposition of ferric acetylacetonate [Fe(acac)₃], in the presence of benzyl ether and phenol, in which inexpensive phenol acted as reducing agent and stabilizer, produce the semi phenol-benzoquinone coated on the Fe₃O₄ and make the Fe₃O₄·MNPs water-soluble and the colloidal solution stable. By changing the molar ratio of phenol to Fe(acac)₃ and reaction time, the size of Fe₃O₄·MNPs could be varied from 19.3 ± 4.4 nm to 9.7 ± 1.5 nm, with the saturation magnetizations in the range of 51.3–62.9 emu/g.     

Proton-acceptor and proton-donor properties of phenol and its substitutes

The donor-acceptor ability of phenols (phenol, 4-chlorphenol, 4-methylphenol, 4-bromphenol, hydroquinone, 4-methyl, and 2-aminophenol) and their complexes with water are investigated by the quantum-chemical method. Incorporation of NH₂ and CH₃ substitutes in the phenol molecule leads to the intensification of the electron density transfer on the carbon atoms of the aromatic ring. The formation of the planar complex increases, and the formation of the nonplanar complex, on the contrary, decreases the proton-acceptor ability of phenols in the ground state. The formation of the nonplanar complex leads to an increase in the proton-donor properties of phenols under excitation. The incorporation of the chlorine atom into the para-position results in the dependence of the donor-acceptor properties of the molecule on the excitation energy. The incorporation of OH-and CH₃-groups in para-position does not influence the proton-donor properties of the isolated phenol molecule. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 28–33, December, 2005.     

流动注射-化学发光法定量测定同一水域中的腐殖酸

采用流动注射-化学发光(FI-CL)这一灵敏的检测方法,通过条件实验与参数优化,优选了测定环境中痕量多羟基酚类化合物的发光体系,通过考察天然水体中的腐殖酸对化学发光-多羟基酚测定体系的影响,为来自于水及土壤中的实际样品中腐殖酸的检测提供了参考,建立了同一区域水体中腐殖酸的化学发光定量测定方法。 所得线性回归方程y=70.36x+540.1,相关系数r=0.995 4,线性范围为3～15 mg·L-1,检测限为0.749 mg·L-1,HA浓度为6 mg·L-1时的相对标准偏差(RSD)为1.08%。     

Fluorescence Characteristics of Schiff Bases Derived from Amino- and Aminoalkylpyridines

The fluorescence characteristics of the Schiff bases 2-(3-pyridylmethyliminornethyl)phenol (1), 2-(2 pyridyliminomethyl)phenol (2), N.N-bis(salicylidene)-2,3-pyridinediamine (3), N,N'-bis(salicylidene)-2,6-pyridinediamine (4) and 2-(2-amino-4-methoxymethyl-6-methyl-3-pyridylmethyliminomethyl)phenol (5) were studied in various solvents at different pH values. Corresponding quantum efficiencies were determined. Compound 1, which showed a tendency towards tautomeric mterconversion to ketoamine in polar protic solvents, was not fluorescent at pH < 8. The fluorescence of other compounds was very sensitive to solvent polarity and the pH of the medium. Compounds 2-4, preferably present as enolimines in all solvents, were not fluorescent in non-polar and moderately polar solvents, whereas weak emission was observed in polar solvents, like methanol, dimethylformamide and dioxane/water 1/1 (0.001 < Q < 0.072). A significant increase in Stokes shifts and in quantum efficiencies was noted as a result of increasing polarity of dioxane/water mixtures, indicating specific interactions with polar water molecules. The emission was promoted at acidic pH values where a pyridinium cation was formed (0.061 < Q < 0.519, in dioxane/water 1/1 at pH 3.4). Compound 5, which was a tautomeric mixture of enoiimine and cyclic diamine in all solvents, was fluorescent in polar as well as in non-polar media. The quantum efficiency varied dependent on the solvent and pH (0.023 <Q< 0.435). The cyclic diamine, i. e. the more rigid structure was supposed to be responsible for the fluorescence in non-polar and aprotic solvents as well as at neutral, and weakly basic pH values.     

Phenol degradation under visible light irradiation in the continuous system of photocatalysis and sonolysis

The combination of photocatalysis under visible light irradiation and sonolysis in the continuous system has been used to degrade an aqueous solution of phenol. ZnFe₂O₄/TiO₂–GAC was employed as the photocatalysts which were obtained by sol–gel process and characterized by spectroscopic X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray microanalyses (SEM–EDX) and Brunauer–Emmett–Teller sorptometer (BET). It was observed that the rates of phenol degradation were affected by the initial pH value of phenol solution, salt addition, gas supplying and the recycling times of the recovered photocatalyst. The kinetic law for the phenol degradation can be apparently expressed as the first-order with respect to the concentration of phenol. Degradation of phenol solution in the continuous system, i.e., photocatalysis and sonolysis has synergistic effect in comparison with the photocatalytic reaction and sonolysis, respectively.     

Dephenolization,dearomatization and detoxification of olive mill wastewater with sonication combined with additives and radical scavengers

In this study, the effects of some additives [manganese (III) oxide (Mn₃O₄), Cu⁺², Fe⁰ and potassium iodate (KIO₃)] and some radical scavengers [sodium carbonate (Na₂CO₃), perfluorohexane (C₆F₁₄) and t-butyl alcohol (C₄H₁₀O)] on the sonication of olive mill effluent wastewater (OMW) were investigated since the wastewaters of this industry are removed with low efficiencies. The maximum total phenol and total aromatic amines (TAAs) removal efficiencies were 88% and 79%, respectively, at 60 °C with only 150 min sonication. The maximum phenol removal was found as 98% with 19 mg L⁻¹ perfluorohexane and 5 mg L⁻¹ Fe⁰ while the maximum TAAs removal was 99% with 16 mg L⁻¹ KIO₃. Catechol, tyrosol, quercetin, caffeic acid, 4-methyl catechol, 2-phenylphenol (2-PHE) and 3-phenyl phenol (3-PHE) were detected as phenol intermediates while trimethlyaniline, aniline, o-toluidine, o-anisidine, dimethylaniline, ethylbenzene and durene were identified as TAAs in the OMW. The maximum acute toxicity removals were 96% and 99% in Vibrio fischeri and Daphnia magna, respectively. Total phenol, TAAs and the toxicity in an OMW were removed efficiently and cost-effectively through sonication.     

Enhancement of sonochemical degradation of phenol using hydrogen atom scavengers

Sonochemical degradation of phenol was found to be enhanced in the presence of the volatile hydrogen atom scavengers CCl4 and perfluorohexane. The non-volatile hydrogen atom scavenger iodate did not enhance phenol degradation. The first order rate constant for aqueous phenol degradation in separate experiments using different sonochemical probes increased in the presence of 150 microM CCl4 from 0.014 to 0.031 min(-1) (probe 1) and from 0.022 to 0.061 min(-1) (probe 2). In the presence of <1.5 microM C6H14, the first order rate constant increased from 0.014 to 0.032 min(-1) (probe 1). Hydroquinone was the major observed reaction intermediate both in the presence and absence of hydrogen atom scavengers. Hydroquinone yields were substantially higher in the presence of hydrogen atom scavengers, suggesting that hydroxyl radical pathways for phenol degradation were enhanced by the hydrogen atom scavengers. These additives may be useful in improving pollutant degradation efficiency or improving synthetic processes that rely on hydroxyl radical as a key intermediate.     

Studies on the surface modification of diatomite with polyethyleneimine and trapping effect of the modified diatomite for phenol

The adsorption isotherm of polyethyleneimine (PEI) on diatomite was studied using UV spectrophotometry, the surface of diatomite was modified with polyethyleneimine by using impregnation method, and the trapping behavior of the modified diatomite for phenol was investigated by using 4-aminoantipyrine (4-AAP) spectrophotometric method. The experiment results show that negatively charged diatomite particles have very strong absorption effect for cationic macromolecule PEI, the adsorption isotherm fits in Freundlich equation. The character that there is a maximum value after intitial sharp increase of adsorption capacity on the adsorption curve indicates that there is strong affinity between diatomite particles and polyethyleneimine macromolecules, and it attributes to the strong electrostatic interaction. After modification with PEI, the electric property of diatomite particle surface changes essentially, and the isoelectric point of diatomite particles moves from pH 2.0 to 10.5. In acidic solution, phenol exists as molecular state, and the modified diatomite particles adsorb phenol through hydrogen bond interaction. However, the hydrogen bond interaction between nitrogen atoms on PEI chains and phenol is weaker because of high degree of protonation of polyethyleneimine macromolecules, so the adsorption quantity is lower. In basic solution, phenol exists as negative benzene–oxygen ion, and the modified diatomite particles adsorb phenol through electrostatic interaction. However, the electrostatic interaction between PEI and negative benzene–oxygen ion is very weak because of low degree of protonation of polyethyleneimine macromolecules, so the adsorption quantity is much lower. The modified diatomite particles produce very strong trapping effect for phenol in neutral aqueous solution via the cooperating of strong electrostatic interaction and hydrogen bond interaction, and the saturated adsorption capacity can attain to 92 mg g⁻¹.     

Co<Subscript>3</Subscript>O<Subscript>4</Subscript> @ PFR cube-like core–shell nanocomposite prepared via a facile one-step hydrothermal approach

The Co₃O₄ @ phenol formaldehyde resin (PFR) cube-like nanocomposites are prepared by one-step hydrothermal process at 120–180 °C for 3–9 h. Co(NO₃)₂·6H₂O, hexamethylenetetramine (HMT), and phenol are used as precursors in water solvent. Any adventitious oxidants and additives are not presented. The transmission/scanning electronic microscope (TEM, SEM) images show as-obtained typical samples are consisted of cube-like Co₃O₄ as core and PFR as shell. The X-ray diffraction (XRD) data indicate the samples are consisted of cube-phase Co₃O₄ with amorphous PFR. Fourier transform infrared spectra (FTIR) further confirm Co₃O₄ and PFR are contained in the samples. Room-temperature vibration magnetic strength measurements (VMS) indicate that the antiferromagnetic properties of core–shell nanocomposites evidently differ from the naked-Co₃O₄ nanoparticles.     

气液两相流滑动弧放电降解苯酚废水

研究了多种因素对气液两相流滑动弧放电降解苯酚废水效果的影响,提高放电电压可提高苯酚的降解效果,在电极间最窄处距离等于3mm时,200mg/L苯酚废水达到最大降解率96%。提高或降低废水的批批pH值及采用氧气作为载气均可提高废水中苯酚的降解效果。     

Ultrasonic waste-water treatment: incidence of ultrasonic frequency on the rate of phenol and carbon tetrachloride degradation

Organic compounds in aqueous solution submitted to an ultrasonic irradiation behave differently according to their physical and chemical properties. In this work, hydrogen peroxide formation and the degradation rate of phenol and carbon tetrachloride have been studied at different frequencies: 20, 200, 500 and 800 kHz. Whatever the frequency, it is easier to decompose CCl₄ than phenol by means of ultrasonic wave. It is shown that the rates of reactions involving hydroxyl radicals (hydrogen peroxide formation and phenol degradation) have a maximum value at 200 kHz. The best yield observed at 200 kHz for the phenol degradation may be the result of better HO radicals availability outside of the bubble of cavitation. The degradation rate for carbon tetrachloride which decomposes into the bubble of cavitation increases with frequency. Calculating the reaction rate for one ultrasonic period shows that the efficiency of one ultrasonic cycle decreases as frequency increases.     

Catalytic mechanisms of potassium salts on pyrolysis of β-O-4 type lignin model polymer based on DFT study

In this study, the possible catalytic mechanisms of potassium salts on lignin pyrolysis was investigated with two β-O-4 type lignin model dimers with different oxygen functional groups on C_α using density functional theory (DFT) calculations. It was found that potassium salts (such as KOH and K₂CO₃) can react with phenol hydroxyl in lignin to form organic-K and further catalyze pyrolysis progress. Through this catalytic mechanism, potassium salts promoted the removal of C_α on specific intermediates and the demethylation of methoxy groups during β-O-4 type lignin pyrolysis, promoted the decomposition of intermediates, and facilitated the formation of phenol and CO₂.     

Low-temperature preparation of anatase titania-coated magnetite

A composite photocatalyst with an anatase titania shell and a magnetite core was prepared in a novel way at low temperature (75 °C at most) by coating photoactive titanium dioxide onto a magnetic Fe₃O₄ core. The photocatalytic activity of the prepared photocatalyst was evaluated by the degradation of model contaminated water of phenol and compared to single-phase titania (either Degussa P25 or prepared titania without magnetic Fe₃O₄). The results showed that the photoactivity was slightly depressed. Then, a remarkable improvement in photoactivity was achieved by modifying the photocatalyst with a SiO₂ layer between the Fe₃O₄ core and TiO₂ shell. The repetitive using of the modified photocatalyst was also investigated, and experimental results illustrated that the photocatalytic-degraded ratio of phenol was still higher than 80% after six cycles.     

Ultrasonic-assisted synthesis of the nanostructures of a Co(II) metal organic framework as a highly sensitive fluorescence probe of phenol derivatives

Nanostructures of a metal-organic framework with chemical formula, [Co(BDC)(L*)]_n.DMF (TMU-40), BDC = 1,4-benzendicarboxylate, L* = 5,6-dipyridin-4-yl-1,2,3,4-tetrahydropyrazine, under ultrasonic irradiation at ambient temperature and atmospheric pressure were prepared and characterized by Fourier-transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). Sonication time, concentration of initial reagents and ultrasonic generator power effects on the size and morphology of nano-structured compounds were studied. TMU-40 (for Tarbiat Modares University) displayed a good potential as a luminescent sensor against phenol derivatives consist of phenol, 4-aminophenol, 4-methylphenol and 4-chlorophenol. Nano-sized TMU-40 showed the better sensing performance in comparison to its bulk phase. The nano TMU-40 displayed very selective and sensitive in detection of phenol derivatives. The detection limit amounts of 15 nM and 63 nM were achieved for 4-aminophenol in nano TMU-40 and bulk TMU-40, respectively. The special structure and fluorescent character of L* ligand and high surface area of nano MOF provide an effective interaction between MOF and phenolic analytes to selectively and sensitively detect of the analyte molecules.     

赤霞珠酿酒葡萄总酚含量的近红外光谱定量分析

酿酒葡萄中的总酚含量是影响葡萄品质的重要指标,也是影响葡萄酒质量的关键因素.为了快速准确地检测赤霞珠葡萄的总酚含量,利用近红外光谱技术结合GA-ELM预测模型对赤霞珠葡萄总酚含量进行预测研究.试验采用5个收获期(每期采集40串,每串取10个)的赤霞珠葡萄,采集200组葡萄的12500～4000 cm-1波段范围内的近红...     

活性炭负载硅钼钒杂多酸催化苯羟基化反应

以活性炭为载体,采用回流吸附法制备了负载型硅钼钒杂多酸催化剂,以冰醋酸作溶剂,过氧化氢作氧化剂,研究了由苯直接羟基化制苯酚的催化活性。结果表明,苯为2mL,冰醋酸为15mL,过氧化氢为5mL,当负载型杂多酸的用量为0.2g、反应温度70℃、反应时间60m in时,硅钼钒催化合成苯酚的收率可达7.4%,选择性达97.1%。