Investigation of the binding and simultaneous quantifications of propanil and bromoxynil herbicide concentrations in human serum albumin

This study reported the use of UV–visible and fluorescence spectroscopy and partial-least-square (PLS) multivariate regression for accurate and simultaneous quantifications of two widely used herbicides, propanil, 3′,4′-dichloropropionanilide (PPL) and bromoxynil, 3,5-dibromo-4-hydroxybenzonitrile (BXL) in human serum albumin (HSA) at physiological conditions. The binding affinity and thermodynamic properties of PPL-HSA and BXL-HSA complexes were also investigated. Partial-least-square (PLS) regression was used to collate the variability in the absorption or emission spectra of PPL-HSA and BXL-HSA complexes with PPL and/or BXL concentrations in HSA samples. The binding constants of 7.66× 10⁸ M^?1 for PPL-HSA and 4.88× 10⁶ M^?1 for BXL-HSA complexes were calculated at physiological conditions (temperature, 310 K; pH 7.4). Thermodynamic parameter values: enthalpy (ΔH) (13.99 kJ mol^?1), entropy (ΔS) (0.078 kJ mol^?1 K^?1), and Gibbs free energy (ΔG) (?10.19 kJ mol^?1) were determined for PPL-HSA complexation at physiological conditions. However, differences in thermodynamic property values of: ΔH (?214.3 kJ mol^?1), ΔS (?0.563 kJ mol^?1 K^?1), and ΔG (?39.70 kJ mol^?1) were observed for BXL–HSA complexes. The binding constants and negative ΔG values indicated strong binding affinity and thermodynamically favorability of PPL–HSA and BXL–HSA complex formation. Results of the PLS regression calibration showed good linearity (R² ≥ 0.998289), high sensitivity, and impressive low limit-of-detections (LODs) of 1.38× 10^?8 M for PPL and 1.68× 10^?8 M for BXL that are comparable and/or lower than many previously reported LODs for herbicide and pesticide analyses. Most importantly, PLS regression is capable of simultaneous quantifications of PPL and BXL concentrations in HSA samples with good accuracy and low errors of 3.66%. UV–visible spectrophotometers and spectrofluorometers are fairly inexpensive, easy to use, and are readily available in almost every laboratory, making this protocol excellent and affordable for routine analysis of weed/pest control chemical residues in humans. The results of this study are significant and remarkable that will provide critical insight into the binding mechanism of herbicide toxicity in humans and non-target organisms, which are of special interest in the area of biomedical study, environmental risk assessment, and ecotoxicology.     

Direct spectral analysis and determination of high content of carcinogenic bromine in bread using UV pulsed laser induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) was applied for the detection of carcinogenic elements like bromine in four representative brands of loaf bread samples and the measured bromine concentrations were 352, 157, 451, and 311 ppm, using Br I (827.2 nm) atomic transition line as the finger print atomic transition. Our LIBS system is equipped with a pulsed laser of wavelength 266 nm with energy 25 mJ pulse^?1, 8 ns pulse duration, 20 Hz repetition rate, and a gated ICCD camera. The LIBS system was calibrated with the standards of known concentrations in the sample (bread) matrix and such plot is linear in 20–500 ppm range. The capability of our system in terms of limit of detection and relative accuracy with respect to the standard inductively coupled plasma mass spectrometry (ICPMS) technique was evaluated and these values were 5.09 ppm and 0.01–0.05, respectively, which ensures the applicability of our system for Br trace level detection, and LIBS results are in excellent agreement with that of ICPMS results.     

铅试金富集——原子吸收光谱法测定锡及锡合金废料的金含量

以火焰原子吸收光谱法测定锡及锡合金废料中的微量元素金。为消除测定过程中各种杂质干扰,采用铅试金法富集样品中的金,实现金与主体锡和其他杂质的分离,通过灰吹后得到金银合金,再以稀硝酸——王水溶解金银合金,在5％的盐酸介质中,以空气-乙炔火焰原子吸收光谱法测定锡及锡合金废料中的金含量。本方法相对标准偏差小于1．5％,加标回收率大于98．0％。     

三维荧光区域积分评估城市污水中溶解性有机物去除

以三维荧光技术为手段,结合荧光区域积分和聚类分析,考察某城市污水厂污水处理过程中溶解性有机物的去除状况。研究结果表明,采用三维荧光区域积分可以表征城市污水中易降解、可降解和难降解有机物相对含量的变化趋势,能够有效识别污水中溶解性有机物的指纹特征。城市污水中类蛋白等易降解物质含量约占总荧光物质的50%,在污水厂曝气池缺氧段,易降解基质被大量去除。曝气池顺水流方向约225 m处,溶解性有机物的去除已基本完成。三维荧光光谱中区域II和III的积分标准体积与TOC的皮尔森相关指数分别为0.964和0.970。和其他荧光指数相比,这2个区域的积分标准体积与TOC的相关度更高。     

Modeling the mobility of glyphosate from two contrasting agricultural soils in laboratory column experiments

The method of single-strand conformational polymorphism (SSCP) was modified in our laboratories for the characterization of baculoviruses, insect viruses with great potential for use as bioinsecticides in biological protection programs. A series of primers were synthesized after the comparison of the polyhedrin gene sequences of over 20 baculoviruses. Polyhedrin is a highly conserved protein which is responsible for the persistence of the virus in the environment. Universal primers were designed which could be used in polymerase chain reactions (PCR) containing genomic DNA from an array of nucleopolyhedrosis viruses (NPVs) including these which are used as biopesticides against important pests of forests and crops, such as Anticarsia gemmatalis, Spodoptera frugiperda, Lymantria dispar, Lymantria monacha and many others. PCR products were denatured and subjected to single-strand DNA electrophoresis at variable temperatures (MSSCP) where, after silver staining, they gave ssDNA band patterns characteristic for each baculovirus species. This technique can be potentially applied to detect baculoviruses in insects collected in the field, as well as to plant tissues and the excrements or bodies of predators without need for sequencing the PCR products. Sometimes MSSCP can be used not only for species determination but also as an indication of genomic variability which can be related to infectivity.     

Raman and SERS spectra of thiamethoxam and the Ag3–thiamethoxam complex: an experimental and theoretical investigation

Dutch water boards have a well-established program for monitoring pesticide contamination of surface waters. These monitoring data have been processed into a graphic format accessible online and designed to provide insight into pesticide presence in Dutch surface waters and trends over time: the Pesticides Atlas (http://www.pesticidesatlas.nl). With this tool one can easily get maps of where a pesticide is being measured and where it might possibly constitute an environmental problem over the years. Presently, results of the periods 1997/1998 until 2005/2006 are available at the level of individual active ingredients. At a national level, the percentage of pesticides concentrations that exceed the maximum tolerable risk has declined 30% to 38% over the years 2003/2004 compared with 1997/1998. This means that surface water quality in the Netherlands has improved with respect to pesticides, however there are still many locations at which the measured concentrations exceed the environmental quality standards. The results on linking land use to pesticides concentrations were shown to assist in optimization of monitoring programs. By developing the present Internet tool, many new opportunities for environmental risk assessment and risk management were identified, e.g. optimization of monitoring strategies and communication to policymakers.     

Selenium speciation and localization in chironomids from lakes receiving treated metal mine effluent

A lake system in northern Saskatchewan receiving treated metal mine and mill effluent contains elevated levels of selenium (Se). An important step in the trophic transfer of Se is the bioaccumulation of Se by benthic invertebrates, especially primary consumers serving as a food source for higher trophic level organisms. Chironomids, ubiquitous components of many northern aquatic ecosystems, were sampled at lakes downstream of the milling operation and were found to contain Se concentrations ranging from 7 to 80 mg kg⁻¹ dry weight. For comparison, laboratory-reared Chironomus dilutus were exposed to waterborne selenate, selenite, or seleno-DL-methionine under laboratory conditions at the average total Se concentrations found in lakes near the operation. Similarities in Se localization and speciation in laboratory and field chironomids were observed using synchrotron-based X-ray fluorescence (XRF) imaging and X-ray absorption spectroscopy (XAS). Selenium localized primarily in the head capsule, brain, salivary glands and gut lining, with organic Se species modeled as selenocystine and selenomethionine being the most abundant. Similarities between field chironomids and C. dilutus exposed in the laboratory to waterborne selenomethionine suggest that selenomethionine-like species are most readily accumulated, whether from diet or water.     

长江重庆段溶解性有机物的荧光特性分析

利用三维荧光光谱(EEMs),并结合平行因子分析(PARAFAC)及主成分分析(PCA),研究了长江重庆段溶解有机物(DOM)的荧光组分特征及其污染来源,并探讨了荧光强度同溶解性有机碳(DOC)及溶解氧(DO)的相关性.结果表明,PARAFAC模型识别出长江重庆段DOM由2类6个荧光组分组成,即类腐殖质荧光组分C1(350/422 nm)、C4(245,305/395 nm)、C5(260,340/420 nm)、C6(260/480 nm)及类蛋白荧光组分C2(275/300 nm)、C3(227,278/329 nm).在DOM来源组成中,陆源的类腐殖质含量占62.56%,类蛋白物质含量占31.31%.类腐殖质组分的荧光强度同DOC的含量存在明显的线性正相关(r=0.73),类蛋白组分的荧光强度同DO的含量呈明显的线性负相关(r=0.80).EEMs-PARAFAC不仅可以表征长江重庆段DOM的光谱特征,示踪长江重庆段的有机污染程度,还可以为三峡库区水体保护提供依据.     

火焰原子吸收分光光度法测定总铬的研究

用火焰原子吸收分光光度法直接测定水和废水中的总铬.通过不同条件的实验,确定了最佳的分析条件;并通过标准样品和实际样品的分析,验证了方法的准确度和精密度.在大量实验基础上,建立空白实验、准确度质量控制图,以便定期对各种监测数据提供可行的质量保证措施.实验结果表明,该法快速方便,提高了分析效率,准确度高,精密度好,值得普及和推广.     

同步荧光光谱法测定环境水样中的多环芳烃

为了建立快速测定水体中多环芳烃的方法,用恒波长同步荧光法对14种多环芳烃混合标样进行了分析。在优化的实验条件下,对环境水样进行分析,可以鉴别出11种多环芳烃。14种PAHs在0～1000ng/ml范围内呈良好的线性关系,相关系数r均不小于0.9988,相对标准偏差(RSD)在1.06%～1.67%之间(n=6)。14种PAHs的检出限在0.072～3.9ng/ml之间。该方法应用于污水、样河水样、池塘水样中的多环芳烃检测取得了良好的效果,回收率分别为82.2%～111.0%、86.0%～107.0%、88.0%～106.2%(n=5)。