银掺杂聚L-甲硫氨酸修饰电极同时测定对苯二酚和邻苯二酚

用循环伏安法制备了银掺杂聚L-甲硫氨酸修饰玻碳电极,研究了对苯二酚和邻苯二酚在该修饰电极上的电化学行为,建立了同时测定对苯二酚和邻苯二酚的新方法.研究发现,在pH=5.0的磷酸盐缓冲溶液中,扫速为100 mV/s时,对苯二酚和邻苯二酚在银掺杂聚L-甲硫氨酸修饰玻碳电极上均出现1对氧化还原峰,峰电位分别为:Epa=0.228 V、Epc =0.162 V和Epa=0.347 V、Epc =0.287 V,二者的氧化峰电位差达119 mV,还原峰差达125 mV.在最佳的条件下,用差分脉冲伏安法同时测定邻苯二酚和对苯二酚的线性范围为3.00 ×10-6～1.00 ×10-4mol/L,检出限为8.0×10-7 mol/L(对苯二酚)和5.0×10-7 mol/L(邻苯二酚).此法用于废水样中对苯二酚和邻苯二酚的测定,获得满意结果.     

特丁基对苯二酚对生物柴油的抗氧化性能研究

生物柴油的氧化安定性是确保生物柴油品质的关键因素。本文采用欧盟标准(EN14214-2002),使用瑞士万通公司生产的873型生物柴油氧化安定性测定仪,采用在植物油抗氧化方面最常用、最有效的特丁基对苯二酚(TBHQ)对由地沟油、大豆油和棉籽油制成的生物柴油的抗氧化性进行了系统的定量研究。结果表明,当添加量大于0.6‰时,3种生物柴油抗氧化时间均超过国标规定的6h。TBHQ是一种理想的生物柴油抗氧化剂,对比另一种常用的抗氧化剂BHA(叔丁基对羟基茴香醚)抗氧化性能优势明显。     

荧光光度法同时测定邻苯二酚、间苯二酚与对苯二酚

将一种直接信号校正(DOSC)-小波包变换(WPT)-偏最小二乘法(PLS)(DOSC-WPT-PLS)新方法用于解析荧光光谱严重重叠的邻苯二酚?间苯二酚和对苯二酚混合物,并对其进行测定。该法将DOSC、WPT及PLS 3种方法结合从而提高了获取特征信息的能力和回归质量。DOSC方法用于除去与浓度无关的结构噪音。利用WPT的时域和频域局部化的特点改进了除噪质量和数据压缩及信息提取能力。PLS方法用于多变量校准和噪音消除。处理该3种组分的荧光光谱数据,并实现了3种化合物的同时测定。设计了PDOSCWPTPLS程序执行相关计算,并对以上3种化学计量学方法进行了比较,其总体相对预测标准偏差分别为4.3%、7.7%、11.5%,结果表明DOSC-WPT-PLS法优于WPT-PLS法和PLS法。将该法用于测定自来水中邻苯二酚?间苯二酚和对苯二酚的含量,其回收率分别为99%~110%?95%~108%和98%~104%,结果满意。     

Recent developments and applications of screen-printed electrodes in environmental assays—A review

Screen-printed electrodes (SPEs), which are used as economical electrochemical substrates, have gone through significant improvements over the past few decades with respect to both their format and their printing materials. Because of their advantageous material properties, such as disposability, simplicity, and rapid responses, SPEs have been successfully utilised for the rapid in situ analysis of environmental pollutants. This critical review describes the basic fabrication principles, the configuration designs of SPEs and the hybrid analytical techniques based on SPEs. We mainly overview the electrochemical applications of SPEs in environmental analysis over the past 3 years, including the determination of organic compounds, heavy metals and gas pollutants.     

Efficient additives to improve the catalytic effects of ferric(III) chloride on the reaction of N‐vinylcarbazole: hydroquinone for methanolysis,hydrogen peroxide for cyclobutanation respectively

Hydroquinone combined with FeCl₃ can reduce the methanolysis time of N‐vinylcarbazole in CH₃OH from 9 h to 1 h, but the addition of hydroquinone to Fe(NO₃)₃ will slow the methanolysis and quench the cyclobutanation process. The addition of H₂O₂ successfully made the FeCl₃ catalytic cyclobutanization of N‐vinylcarbazole in the yield from zero up to 33%. Copyright © 2011 John Wiley & Sons, Ltd.     

Phase transitions in the hydroquinone hydrogen sulfide clathrate compound

Heat capacities of [C₆H₄(OH)₂]₃·(H₂S) _x were measured between 1 and 15 K. Heat capacity peaks were found at (7.56±0.09) K, (7.61±0.05) K, and (7.65±0.07) K for the compounds withx=0.92, 0.95, and 0.96. A weak anomaly was observed around 6.75 K for the compound withx=0.85. The temperatures of these anomalies are unusually low among the phase transitions of molecular crystals. The decrease of the transition temperature from that of crystalline H₂S (=103.52 K) is a clear indication of the effect of enclathration on the molecular interaction. A comparison of the rotational heat capacity of the trapped hydrogen sulfide molecules with that of crystalline hydrogen sulfide shows that the trapped hydrogen sulfide molecules have a large rotational freedom at low temperatures (13 K). This agrees with the results from far infrared spectroscopic data. The dielectric constant of the clathrate compound obeyed the Curie-Weiss law above 30 K and no significant dielectric loss was found over the whole temperature range. These results showed that the trapped hydrogen sulfide molecules execute free rotation or are orientationally disordered above 20 K.Dedicated to Professor H. M. Powell.     

NMR assignment in regioisomeric hydroquinones

A set of regioisomeric pairs of tricyclic hydroquinones, analogues of antitumor 9,10-dihydroxy-4,4-dimethyl-5,8-dihydroanthracen-1(4H)-one (1) and other derivatives, were synthesized and their regiochemistry and NMR spectra assigned by using (1)H-detected one-bond (C-H) HMQC and long-range C-H HMBC, in good agreement with theoretical O3LYP/Alhrichs-pVTZ calculations. The 5-hydroxymethyl derivatives (11, 15, 19) showed a (3)J(H, H) coupling constant of methylene protons evidencing the presence of a seven-membered intramolecular hydrogen bonded ring, not observed for the 8-hydroxymethyl isomers.     

Influence of the bisphenol structure on the direct synthesis of sulfonated poly(arylene ether) copolymers. I

New sulfonated poly(arylene ether sulfone) copolymers with high molecular weights were successfully synthesized with controlled degrees of disulfonation of up to 70 mol % via the direct copolymerization of sulfonated aromatic dihalides, aromatic dihalides, and one of four structurally distinct bisphenols. The disodium salts of the 3,3′‐disulfonated‐4,4′‐dichlorodiphenyl sulfone and 3,3′‐disulfonated‐4,4′‐difluorodiphenyl sulfone comonomers were synthesized via the sulfonation of 4,4′‐dichlorodiphenyl sulfone or 4,4′‐difluorodiphenyl sulfone with 30% fuming sulfuric acid at 110 °C. Four bisphenols (4,4′‐bisphenol A, 4,4′‐bisphenol AF, 4,4′‐biphenol, and hydroquinone) were investigated for the syntheses of novel copolymers with controlled degrees of sulfonation. The composition and incorporation of the sulfonated repeat unit into the copolymers were confirmed by ¹H NMR and Fourier transform infrared spectroscopy. Solubility tests on the sulfonated copolymers confirmed that no crosslinking and probably no branching occurred during the copolymerizations. Tough, ductile films were solvent‐cast that exhibited increased water absorption with increasing degrees of sulfonation. These copolymers are promising candidates for high temperature proton‐exchange membranes in fuel cells, which will be reported separately in part II of this series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2264–2276, 2003