Organic-phase enzyme electrode for phenolic determination based on a functionalized sol-gel composite

An amperometric biosensor for monitoring phenols in the organic phase was constructed by the silica sol-gel immobilization of tyrosinase on a glassy carbon electrode. The organic-inorganic hybrid materials with different sol-gel precursors and polymers were optimized, and the experimental conditions, such as the effect of the solvent, operational potential and enzyme loading were explored for the optimum analytical performance of the enzyme electrode. The biosensor can reach 95% of steady-state current in about 18 s, and the trend in the sensitivity of different phenols is as follows: catechol > phenol >p-cresol. In addition, the apparent Michaelis-Menten constants (K-m(app)) and the stability of the enzyme electrode were discussed. (C) 2000 Elsevier Science S.A. All rights reserved.

Bright green organic electroluminescent devices based on a novel thermally stable terbium complex

A navel thermally stable terbium carboxylate complex, Tb(MTP)(3)(phen) (MTP=monotetradecyl phthalate, phen=1,10-phehanthroline), was synthesized and characterized. The device structure of glass substrate/indium-tin-oxide/poly(p-phenylenevinylene) (PPV)/poly (N-vinycarbazole) (PVK):Tb(MTP)(3)(phen): 1,3,4-oxadizole derivative (PBD)/tris(8-hydroxyquinoline) (Alq(3))/aluminum (Al) was employed to study the electroluminescent properties of Tb(MTP)(3)(phen). A green emission with extremely sharp spectral band of less than 10 nm at 544 nm peak wavelength was observed. A maximum luminance of 152 cd/m(2) and an external quantum efficiency of 0.017% were achieved at a drive voltage of 24 V. A possible mechanism of energy transfer based on the polymer doped with lanthanide organic complex was also proposed.

The effect of substrate and solvent properties on the response of an organic phase tyrosinase electrode

The responses of a cryohydrogel tyrosinase enzyme electrode to four substrates in three pure water immiscible organic solvents were investigated. Kinetic parameters, the maximum kinetic current, I-max, the apparent Michaelis-Menten constant, K-m(app), and I-max/K-m(app), were calculated. The I-max/K-m(app) value was taken as an indicator of the catalytic efficiency of the sensor. The effect of the substrate hydrophobicity on I-max/K-m(app) and response time of the sensor were discussed. The effects of both hydrophobicity (log P) and dielectric constant (epsilon) of the organic solvent on the catalytic efficiency of the enzyme in the organic phase were studied. (C) 1997 Elsevier Science S.A.

ELECTROCHEMICAL INVESTIGATION OF LIQUID/LIQUID SYSTEMS USING VARIOUS ORGANIC SOLVENTS

The potential windows of the system water/pure solvent (W/P) and water/solvent mixtures(W/S) have been investigated by cyclic voltammetry with solvents whose dielectric constants lie between 5.87 and 34.82. In the presence of LiCI in the aqueous phase and tetrabutytammoniumtetraphenylborate(TBATPB) in the organic phase, the systems water/allyl iso-thiocyanate (W/AIT) and water/nitrobensene (W/NB) show a same wide epotential window. thermodynamic parameters of ion transfer W/AIT interface were determined. In systems of W/P and V/S the influence solvent effect on the standard gibbs energies of transfer of was discussed.

藻体对水环境中N、P及重金属Cu2+、Pb2+、Cd2+、Cr6+的吸附特征研究

随着全球生态环境的恶化，各国日益重视对水体中各种污染物的治理。利用藻类的吸收、富集和降解作用，可以去除污水中的营养物质、重金属离子和有机污染物，与其他物理、化学及工程的方法相比，该技术具有以下优点：成本低、能耗小、治理效果较好，对环境污染小，有利于资源化，有利于整体生态环境的改善，是治理水质污染的新途径。 本文利用几种大型海藻对富营养化海水进行处理，结果发现孔石莼、刚毛藻均有很强的吸收N、P的能力，吸收能力依次为褶曲刚毛藻>束生刚毛藻>孔石莼。水体中褶曲刚毛藻3 g/L含量，在3～5小时之内，可把中等以上富营养化海水中的N、P降低至一类海水水平。利用刚毛藻处理富营养化地下海水和养殖废水，进行海参和大菱鲆养殖试验，探索藻类净化水质和废水循环利用的新模式，使水体保持较低的营养盐状态，减轻养殖废水对环境的影响，实现了海水养殖业与环境的可持续发展。 刚毛藻在我国近海滩涂分布广泛，利用它来处理富营养化水体，并和水产养殖业相结合，既净化水体，使养殖废水能循环利用，满足水产养殖的需求，又改善水产业生态环境。同时，将回收藻体生产优质饲料、食品和药物等，实现藻类资源的高值利用。刚毛藻营养丰富，用其替代鼠尾藻作海参饲料，资源丰富，成本低，效果好，是一种值得加以开发利用的宝贵资源，具有广泛的应用前景。 生物吸附法是一种经济有效的移除废水中有害重金属离子的方法。由于藻类细胞壁中的多聚糖可提供吸附重金属的位点，廉价而蕴藏丰富的海藻对多种重金属表现出很强的吸附能力。所以本文通过分批实验，研究了非活体刚毛藻对水体中重金属Cu2+、Pb2+和Cd2+的吸附影响因子、吸附热力学、吸附动力学及吸附机理，得到了平衡等温线及动力学数据。吸附过程的最佳pH值为5.0，吸附量随温度的升高而增加，水体中常见的Na+、K+、Ca2+、Mg2+阳离子及Cl-、NO3-、SO42-、C2O42-等阴离子的存在对吸附的影响并不显著。EDTA存在时，吸附百分率大大降低。吸附等温线符合Langmuir和Freundlich方程。刚毛藻对重金属Cu2+、Pb2+和Cd2+的吸附容量很高，25℃时，对Cu2+、Pb2+和Cd2+的最大吸附容量分别为1.61 mmol/g、0.96 mmol/g和0.98 mmol/g，且吸附过程为吸热反应。刚毛藻对重金属Cu2+、Pb2+和Cd2+的吸附过程为化学吸附，在吸附过程中藻体表面的官能团可能与金属离子发生了螯合作用。吸附动力学过程符合pseudo-二级动力学模型，在初始的30min内，吸附速率很快，随后速率逐渐降低。解吸试验表明，用EDTA可以对重金属进行回收，刚毛藻可以循环利用。实验结果表明刚毛藻是一种高效、经济实用的生物吸附材料，可用来吸附回收水体中的重金属Cu2+、Pb2+和Cd2+等。 通过非活体刚毛藻对重金属Cr6+的吸附影响因子、吸附动力学、吸附机理的研究发现，刚毛藻对Cr6+具有很强的还原能力，对电镀废水中的Cr6+的还原去除提供了非常好的方法。吸附过程的最佳pH值为2～3，实际电镀废水通常在此pH范围，因此处理实际废水时，首先在原酸性条件下，对Cr6+进行还原去除，然后调废水pH至5.0，继续进行吸附，去除其他二价离子及被还原的三价Cr离子，实现了利用同一材料还原Cr6+为Cr3+，并将Cr3+和其他重金属离子同时去除。通过对机理的讨论，认为刚毛藻对Cr6+的生物吸附过程不是一个简单的“离子交换过程”，而是一个“吸附还原过程”。在海藻量足够的前提下，只要时间足够长，Cr6+可被彻底还原去除。 利用工业废弃物褐藻渣，对水体中重金属离子Cu2+、Pb2+、Cd2+及Cr6+的生物吸附特性分别进行了讨论，结果表明褐藻渣对重金属离子的吸附特性与刚毛藻一致，吸附等温线符合Langmuir和Freundlich方程，在25℃时，pH为5.0时，由Langmuir方程求出褐藻渣对Cu2+、Pb2+和Cd2+的最大吸附容量分别为4.20 mmol/g、3.13 mmol/g和2.97 mmol/g。褐藻渣对低、高浓度的重金属Cr6+都具有很强的吸附能力，且移除效果比较彻底。实际应用结果表明，褐藻渣是一种高效、经济实用的生物吸附材料，可用来吸附回收水体中的重金属离子，具有广泛的应用前景。

Three-dimensional fluorescence characteristics of dissolved organic matter produced by Prorocentrum donghaiense Lu

Filtration and cross-flow ultrafiltration techniques were used to separate culture media of Prorocentrum donghaiense at the exponential growth, stationary and decline stages into < 0.45 mu m filtrate, 100 kDa-0.45 mu m, 10-100 kDa and 1-10 kDa retentate and < 1 kDa ultrafiltrate fractions. The fluorescence. properties of different molecular weights of dissolved organic matter (DOM) were measured by excitation-emission matrix spectra. Protein-like and humic-like fluorophores were observed in the DOM produced by P. donghaiense. The central positions of protein-like fluorophores showed a red shift with prolonged growth duration, shifting from tyrosine-like properties at the exponential growth stage to tryptophan-like properties at the stationary and decline stages. The excitation wavelengths of protein-like fluorophores exhibited some change in the exponential growth and stationary stages with increased molecular size, but showed little change in the decline stage. However, the emission wavelengths in the decline stage exhibited a blue shift. Very distinct C type and A type peaks in humic-like fluorophores were observed. With a prolonged culture time, the intensities of both of the peaks became strong and the excitation wavelengths of peak A showed a red shift, while the A:C ratios fell. More than 94% of fluorescent DOM was in the lower than 1 kDa molecular weight fraction.

Seasonal changes in the distribution of dissolved organic nitrogen in coastal and open-ocean waters in the North East Pacific: sources and sinks

The distribution of dissolved organic nitrogen (DON) and nitrate were determined seasonally (winter, spring and summer) during three years along line P, i.e. an E-W transect from the coast of British Columbia, Canada, to Station P (50degreesN, 145degreesW) in the subarctic North East Pacific Ocean. In conjunction, DON measurements were made in the Straits of Juan de Fuca and Georgia within an estuarine system connected to the NE Pacific Ocean. The distribution of DON at the surface showed higher values of 4-17 muM in the Straits relative to values of 4-10 muM encountered along line P, respectively. Along line P, the concentration of DON showed an inshore-offshore gradient at the surface with higher values near the coast. The equation for the conservation of DON showed that horizontal transport of DON (inshore-offshore) was much larger than vertical physical mixing. Horizontal advection of DON-rich waters from the coastal estuarine system to the NE Pacific Ocean was likely the cause of the inshore-offshore gradient in the concentration of DON. Although the concentration of DON was very variable in space and time, it increased from winter to summer, with an average build up of 4.3 muM in the Straits and 0.7 muM in the NE subarctic Pacific. This implied seasonal DON sources of 0.3 mmol N m(-2) d(-1) at Station P and 1.5 mmol N m(-2) d(-1) in the Straits, respectively. These seasonal DON accumulation rates corresponded to about 15-20% of the seasonal nitrate uptake and suggested that there was a small seasonal build up of labile DON at the surface. However, the long residence times of 180-1560 d indicated that the most of the DON pool in surface waters was refractory in two very different productivity regimes of the NE Pacific. (C) 2002 Elsevier Science Ltd. All rights reserved.

Influence of methanol on retention of hydrophobic organic chemicals in soil leaching column chromatography

The influence of methanol in methanol-water mixed eluents on the capacity factor (P), an important parameter which could depict leaching potential of hydrophobic organic chemicals (HOCs) in soil leaching column chromatography (SLCC), was investigated. Two reference soils, GSE 17201 obtained from Bayer Landwirtschaftszentrum, Monheim, Germany and SP 14696 from LUFA, Spencer, Germany, were used as packing materials in soil columns, and isocratic elution with methanol-water mixtures at different volume fractions of methanol (phi) were tested. Shortterm exposure of the column (packed with the GSE 17201 soil) to the eluents increased solute retention by a certain (23% log-unit) degree evaluated through a correlation with the retention on the same soil column but unpreconditioned by methanol-containing eluents. Long-term exposure of soil columns to the eluents did not influence the solute retention. A log-linear equation, log k' = log k'(w) - Sphi, could well and generally describe the retention of HOCs in SLCC. For the compounds of homologous series, logk'(w), had good linear relationship with S, indicating the hydrophobic partition mechanism existing in the retention process. (C) 2002 Elsevier Science Ltd. All rights reserved.

Linear solvation energy relationships regarding sorption and retention properties of hydrophobic organic compounds in soil leaching column chromatography

The capacity factors of a series of hydrophobic organic compounds (HOCs) were measured in soil leaching column chromatography (SLCC) on a soil column, and in reversed-phase liquid chromatography on a C-18 column with different volumetric fractions (phi) of methanol in methanol-water mixtures. A general equation of linear solvation energy relationships, log(XYZ) = XYZ(0) + mV(1)/100 + spi* + bbeta(m) + aalpha(m), was applied to analyze capacity factors (k'), soil organic partition coefficients (K-oc) and octanol-water partition coefficients (P). The analyses exhibited high accuracy. The chief solute factors that control log K-oc, log P, and log k' (on soil and on C-18) are the solute size (V-1/100) and hydrogen-bond basicity (beta(m)). Less important solute factors are the dipolarity/polarizability (pi*) and hydrogen-bond acidity (alpha(m)). Log k' on soil and log K-oc have similar signs in four fitting coefficients (m, s, b and a) and similar ratios (m:s:b:a), while log k' on C-18 and log P have similar signs in coefficients (m, s, b and a) and similar ratios (m:s:b:a). Consequently, log k' values on C-18 have good correlations with log P (r > 0.97), while log k' values on soil have good correlations with log K-oc (r > 0.98). Two K-oc estimation methods were developed, one through solute solvatochromic parameters, and the other through correlations with k' on soil. For HOCs, a linear relationship between logarithmic capacity factor and methanol composition in methanol-water mixtures could also be derived in SLCC. (C) 2002 Elsevier Science Ltd. All rights reserved.