对甲酚修饰的超高交联树脂的合成及对4-硝基苯胺的吸附性能

氯球和对甲基酚发生Friedel-Crafts反应制备对甲基酚修饰的超高交联树脂(简记为GQ-03),研究GQ-03树脂对4-硝基苯胺(PNA)的吸附性能。实验结果表明:GQ-03树脂的比表面积高达1154.45m2/g,树脂孔径分布在微孔(0～2nm)、中孔(2～50nm)区;GQ-03树脂对PNA的吸附性能优于商业NDA-88、NDA-99、NDA-150、XAD-4和H103树脂;当溶液pH值在3.1～8.0之间,GQ-03树脂对PNA的吸附量最大;GQ-03树脂对PNA的吸附量随温度的升高而降低,树脂对PNA的吸附等温线符合Freundlich模型;GQ-03树脂对PNA的饱和吸附量为154.41mg/mL,树脂可用8.8BV 80%乙醇和1mol/L HCl混合溶液解吸,解吸率为98.82%。     

Determination of P-Cresol (and Other Phenolics) Using a Conducting Polymer Based Electro-Immunological Sensing System

Abstract

Antibodies to a p-cresol bovine serum albumin conjugate have been produced and incorporated into a conducting polymer to form an electro-immunological sensing system. Using flow injection analysis and pulsed electrochemical detection sensitive, reproducible and rapid responses to p-cresol and other phenolics can be obtained. The sensor is reusable.     

Alkylation of p-cresol with tert-butanol catalyzed by heteropoly acid supported on zirconia catalyst

Butylation of p-cresol by tert-butanol was catalyzed by 12-tungstophosphoric acid supported on zirconia (TPA/ZrO₂) under flow conditions. Catalysts prepared with different TPA loading (5–30 wt.%) were calcined at 1023 K and acidity was estimated by temperature programmed desorption (TPD) of NH₃. Fifteen percent TPA/ZrO₂ showed the highest acidity and found to be the most active catalyst in butylation of p-cresol. The effects of temperature, space velocity (LHSV) and molar ratio of the reactants on the conversion of p-cresol and products selectivities were optimized and the optimum reaction conditions evaluated were 403 K, tert-butanol/p-cresol (Bu/Cr) molar ratio 3 and LHSV 4 h⁻¹. Under the optimized conditions, conversion of p-cresol was found to be 61 mol% with product selectivity for 2-tert-butyl-p-cresol (TBC) 81.4%, 2,6-di-tert-butyl-p-cresol (DTBC) 18.1% and tert-butyl-p-tolyl ether (ether) 0.5%. Study of time on stream (TOS) performed as a function of time for 100 h showed that the loss in activity in terms of conversion of p-cresol was 6%.     

电化学氧化法合成茴香醛（Ⅰ）

介绍了茴香醛的合成和利用。报道了以对甲苯酚为原料，用池外式间接电化学氧化法合成茴香醛的最佳条件。电氧化再生媒质的电流效率达９４．０～９５．０％。     

A STUDY OF SILICA-SUPPORTED CROSS-LINKED POLY (MALEIC ACID-CO-STYRENE)-PLATINUM COMPLEX IN THE HYDROGENATION OF p-CRESOL

A silica-supported cross-linked poly(maleic acid -co- styrene)-platinum complex (PMS-Pt) has been prepared and found to be active in the hydrogenation of p-cresol undermild conditions (303-323K, 1.01×10~5Pa). In this hydrogenation system water servesas a solvent and p-cresol can be converted to 4-methylcyclohexanol quantitatively via4-methylcyclohexanone as intermediate.     

Adsorption of small uremic toxin molecules on MFI type zeolites from aqueous solution

Adsorption properties of zeolites were investigated for the removal of p-cresol from aqueous solutions at 37 °C within the context of studying alternative methods to dialysis for removing uremic toxin from blood. MFI-framework type zeolites with different degrees of hydrophobicity and charge compensating cations were prepared: one pure silica MFI and four alumino-silicate MFIs (Si/Al = 30), with H⁺, Na⁺, K⁺ and Mg²⁺ as charge compensating cations. Adsorption isotherms and microcalorimetric measurements show a high affinity of p-cresol for all MFI type zeolites. The best capacity is obtained for the pure silica MFI, whereas the alumino-silicate samples show a higher affinity in the low concentration range. In the case of pure silica sample, the microscopic adsorption mechanism including the role of confined water is elucidated with the help of NMR, X-ray analysis (including Rietveld refinement) and Monte Carlo simulations. For all samples the high affinity is preserved in physiological serum solution, even in the presence of other toxin molecules such as urea. It is also shown that the compensating cation state of the samples is imposed by the physiological medium.     

常压下由对甲酚催化氢化制备4—甲基环己酮

4-甲基环己酮作为一种优良的有机溶剂及有机合成中间体,在微电子工业及医药、香料、精细化工合成中有很重要的用途。文献报道的各种制备方法中,以对甲酚为原料经催化氢化制备4-甲基环己酮有实际意义。但催化氢化大多在加压情况下进行,所用催化剂多为钯,也有用钉、铑或莱尼镍作催化剂的,但加氢产物多为甲基环己醇,且酮的收率很低。本文采用铑催化剂(以氧化铝作载体),实现了对甲酚的常压催化氢化,制得4-甲基环己酮,并对催化条件作了初步摸索和探讨。     

The Oxidation of Guaiacol,Serotonin, o-Cresol,p-Cresol,m-Cresol,Homovanillic Acid,and m-Tyrosine by Horseradish Peroxidase and Hydrogen Peroxide

Abstract

A survey of 14 substrates for the fluorometric determination of the oxidative enzyme-horseradish peroxidase was carried out. The compounds which seemed to act well as substrates are serotonin, guaiacol, o-cresol, p-cresol, m-cresol, homovanillic acid and m-tyrosine. L-Epinephrine, equilenin, equilin, β-estradiol, estriol, and estrone were studied and found not to be substrates of the system.

The kinetics of the oxidation reactions were studied. They followed the Michaelis constant rate equation. The Michaelis constant, Km, was determined by a Lineweaver-Burk plot for each substrate.

It would appear that the presence of a group in the ortho, para, or meta position of the phenolic ring decreases the binding of the subtrate to the enzyme's active site, as shown by the km values obtained. It may be concluded that m-tyrosine is the best substrate (lowest km value) when compared to all the substrates which have been studied to date by the authors.     

柱前衍生高效液相色谱法分离分析甲酚异构体

提出了柱前衍生高效液相色谱法同时分离测定邻甲酚、间甲酚和对甲酚的方法。含甲酚异构体的样品与衍生化试剂按1比8(质量比)混合,加热回流衍生2 h。3种异构体的转化率依次为98.1%,99.0%,98.5%。选用Eclipse XDB-C_(18)色谱柱作为反相色谱柱,以甲醇和水以体积比为35比65的混合溶液为流动相,在260nm波长处进行测定,乙酸邻甲酚酯、乙酸间甲酚酯的峰面积与其浓度在(0.05～3.75)×10~(-5)mol·L~(-1)范围内呈线性关系,而乙酸对甲酚酯在(0.03～2.25)×10~(-5)mol·L~(-1)之间呈线性关系,检出限(3S/N)依次为1.88×10~(-5),1.88×10~(-5),1.13×10~(-5)mol·L~(-1)。此方法应用于实际样品的测定,回收率分别为104%,95%,100%,相对标准偏差(n=7)分别为0.22%,2.34%,0.90%。     

自支撑CNTs/SMF-Ni电极上电催化氧气氧化茴香醚合成茴香醛

以具有三维开放网络结构的薄层大面积烧结8 μm金属纤维(SMF-Ni, SMF-SS(316L不锈钢))为基底, 通过乙烯催化化学气相沉积在金属纤维表面生长碳纳米管(CNTs)的方法, 制备了整体式CNTs/SMF-Ni (CNTs: 50% (w))和CNTs/SMF-SS (CNTs: 40% (w))复合材料. 研究表明, 以CNTs/SMF-Ni 为阴极材料、SMF-SS为阳极材料, 具有很高的直接电催化氧气氧化对甲氧基甲苯(茴香醚)合成对甲氧基苯甲醛(茴香醛) 的活性, 反应物转化率和产物选择性分别达95.4%和96.5%, 电流效率可超过80%.