邻苯二甲酸二甲酯在离体人红细胞内的分布和含量研究

邻苯二甲酸酯类污染物(PAEs)在环境中普遍存在,可沿食物链富集,危害人体健康。本文利用荧光光谱法和高效液相色谱法(HPLC)探究了邻苯二甲酸二甲酯(DMP)在离体人红细胞内的分布情况。结果表明,红细胞在310 nm、490 nm和609nm处各具有一个荧光特征峰,其来源分别为:红细胞内的蛋白;还原型烟酰胺腺嘌呤二核苷酸磷酸(NADPH)、黄素腺嘌呤二核苷酸(FAD)和膜脂;锌卟啉和原卟啉。DMP染毒后,310 nm处的荧光峰出现明显下降,其原因为进入红细胞内的DMP与蛋白发生了结合;490 nm和609 nm处的荧光峰变化很小。高效液相色谱(HPLC)实验结果表明,DMP能透过红细胞膜进入细胞内部,其进入量随暴露量增加而增加,进入量和暴露量的比值随暴露量增加而减少。上述研究成果能加深对PAEs在血液运输过程中与红细胞毒性作用的理解,可为PAEs的危险性评估和相关疾病预防提供数据参考。     

1H-NMR-based metabolomic studies of bisphenol A in zebrafish (Danio rerio)

Proton nuclear magnetic resonance (¹H-NMR) spectroscopy was used to study the response of zebrafish (Danio rerio) to increasing concentrations of bisphenol A (4,4′-(propane-2,2-diyl)diphenol, BPA). Orthogonal partial least squares discriminant analysis (OPLS-DA) was applied to detect aberrant metabolomic profiles after 72 h of BPA exposure at all levels tested (0.01, 0.1, and 1.0 mg/L). The OPLS-DA score plots showed that BPA exposure caused significant alterations in the metabolome. The metabolomic changes in response to BPA exposure generally exhibited nonlinear patterns, with the exception of reduced levels of several metabolites, including glutamine, inosine, lactate, and succinate. As the level of BPA exposure increased, individual metabolite patterns indicated that the zebrafish metabolome was subjected to severe oxidative stress. Interestingly, ATP levels increased significantly at all levels of BPA exposure. In the present study, we demonstrated the applicability of ¹H-NMR-based metabolomics to identify the discrete nature of metabolic changes.     

BDE-47和BDE-209对乙酰胆碱酯酶(AChE)活性的抑制特性及分子作用力研究

多溴联苯醚(PBDEs)是应用广泛的溴代阻燃剂,其中2,2',4,4'-四溴联苯醚(BDE-47)和2,2',3,3',4,4',5,5',6,6'-十溴联苯醚(BDE-209)广泛存在于环境中。PBDEs具有神经毒性,但其致毒机制尚不明确。本文通过研究BDE-47与BDE-209对乙酰胆碱酯酶(AChE)活性的影响及二者与AChE相互作用的光谱分析,揭示BDE-47与BDE-209导致神经毒性的致毒机制。BDE-47和BDE-209在一定浓度范围内均能够抑制AChE分解乙酰胆碱;随着浓度的增加,两者的抑制率均呈现出先增加后降低的规律。BDE-47浓度为400μmol·L-1时抑制率达到最大,为22.3%;BDE-209浓度为200μmol·L-1时抑制率达到最大,为11.2%。相同浓度下,BDE-47对AChE的抑制率始终大于BDE-209,表明AChE对BDE-47更加敏感。荧光光谱分析结果表明BDE-47和BDE-209与AChE之间的相互作用均主要为疏水作用,同时不存在范德华引力作用;BDE-47与AChE的结合常数大于BDE-209与AChE的结合常数,表明BDE-47更易与AChE相互作用。此外,温度的升高不利于BDE-47和BDE-209与AChE之间相互作用。BDE-47和BDE-209抑制AChE活性很可能是导致神经毒性通路之一。     

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.     

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.     

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％。     

稳恒磁场作用下微生物燃料电池的产电特性和电化学阻抗谱分析

对混合菌接种的双室微生物燃料电池加载磁场强度为175 mT的稳恒磁场,利用电化学交流阻抗等电化学分析方法,考察了在磁场作用下微生物燃料电池（MFC）产电性能的变化,分析了磁场对MFC各部分内阻的影响。加载磁场使已启动完成的MFC的产电明显增强,开路电压提高了10%。加载磁场后最大功率密度为2.08 W/m2,大于加载前的1.58 W/m2,表观内阻由170Ω降至80Ω。电化学阻抗谱分析确定了阳极、阴极和全电池的等效电路模型,拟合结果发现阳极极化内阻约为5Ω。加载磁场使MFC的阴极极化内阻由74.98Ω降至56.73Ω。     

长江重庆段主城水体沉积物溶解性有机质(DOM)的光谱特性

应用荧光发射光谱、荧光激发 发射光谱矩阵（EEMs）结合紫外 可见光吸收光谱对长江重庆段主城水体沉积物溶解性有机质(DOM)的光谱特性进行了研究。通过应用吸收指数E2/E3、荧光指数〖WTBX〗f450/f〖WTBZ〗500和三维荧光光谱特征指纹等参数,对长江重庆段主城水体沉积物溶解性有机质(DOM) 的来源、组成和空间分布规律进行了探讨。结果表明：沉积物溶解性有机质以类胡敏酸为主,其他的类富里酸、水体微生物代谢物质和类蛋白物质均有检出,陆源输入为水体沉积物溶解性有机质(DOM)主要来源,并且荧光强度在空间分布上呈现先升高后降低再升高的趋势     

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.     

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.