持久性有机污染物的植物修复

简要介绍了持久性有机污染物,重点分析了植物对去除环境中持久性有机污染物的修复机制,指出了植物修复技术存在的问题和今后的发展方向。     

The uptake of persistent organic pollutants by plants

In a field experiment, the transfer of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) from contaminated soil to maize (Zea mays L.), sunflower (Helianthus annuus), poplar (Populus nigra × P. maximowiczii) and willow (Salix × smithiana) and the distribution of PCB congeners in maize and sunflower was investigated. The former waste incinerator in Hradec Králové (Czech Republic) was chosen for the experiment. Results of plot screening showed heterogenous contamination by PCBs and PAHs. PCB soil contamination was evidently caused by Delor 106 or Aroclor 1260 stocking and PAH contamination by chemicals containing fluoranthene, benzo/b/fluoranthene, phenanthrene and pyrene. Tested plants were planted on a contaminated field site, in soil contaminated with 1530 μg/kg of total PCBs and 0.138 and 3.42 mg/kg of total PAHs. The results show that maize and sunflower roots accumulated the most PCBs from soil. These plants accumulated hexa- and heptachlorobiphenyl congeners more than tri-, tetra-, and pentachlorobiphenyl congeners. Total concentrations of PAHs in tested plants ranged from 0.096 to 1.34 mg/kg. The highest phenanthrene concentration was found in aboveground biomass of sunflower and the highest concentration of pyrene, in maize roots.     

Electronic structure study using density functional theory in organic dendrimers

The electronic and structural properties of pyrrolic ring derivatives were studied using density functional theory (DFT) in terms of their application as organic semiconductor materials in photovoltaic devices. The B3LYP hybrid functional in combination with Pople type 6-31G(d) basis set with a polarization function was used in order to determine the optimized geometries and the electronic properties of the ground state, while transition energies and excited state properties were obtained from time-dependent (TD)-DFT with B3LYP/6-31G(d) calculation. The investigation of pyrrolic derivatives formed by the arrangement of several monomeric units revealed that three-dimensional (3D) conjugated architectures in which the combination of a triphenylamine (TPA) core with π-conjugated rings attached to the core, present the best geometric and electronic characteristics for use as an organic semiconductor material. The highest occupied molecular orbital (HOMO) − lowest unoccupied molecular orbital (LUMO) energy gap was decreased in 3D-structures that extend the absorption spectrum toward longer wavelengths, revealing a feasible intramolecular charge transfer process in these systems. All calculations in this work were performed using the Gaussian 03 W software package.     

Asparagine deamidation: pH-dependent mechanism from density functional theory

Asparagine deamidation is a decisive event in chemotherapy-induced apoptosis and a major obstacle in the formulation of monoclonal antibodies. Despite the importance of deamidation, little is known about the elementary reactions involved. B3LYP/6-31+G(d,p)/COSMO-RS calculations were used to obtain stable structures and transition states for a network of reactions. Calculated rate constants were incorporated into a kinetic model of the pH dependence and compared to a pseudo-steady-state model. At low pH, the calculations show that deamidation occurs by direct acid-catalyzed hydrolysis to aspartate. At neutral to basic pH, deamidation proceeds by the initial formation of a tetrahedral intermediate. The intermediate can be converted to succinimide by two pathways and three rate-determining steps that shift in relative importance with pH. The calculated pH-dependent rate constant qualitatively agrees with the experimental pH dependence. The rate-determining transition state structures may help to understand chemotherapy-induced apoptosis and improve protein formulations.     

微生物降解持久性有机污染物的研究进展与展望

持久性有机污染物（POPs）是伴随着人类工业化发展而产生的合成类污染物,具有高毒性、持久性、长迁移性和高生物富集性等特点,POPs污染物的微生物降解一直是环境科学与技术应用领域的研究热点。微生物降解技术修复POPs污染环境具有无二次污染、成本低、快速简便等优点,拥有广泛的应用前景。本文论述了各种POPs微生物分解代谢的最新研究进展,包括降解性微生物资源以及降解机制。此外,还讨论了计算生物学、合成生物学、基因组学等技术在POPs微生物降解中的潜力和应用,以期为环境中持久性有机污染物的修复提供参考。     

Removal of persistent organic pollutants from micro-polluted drinking water by triolein embedded absorbent

A new biomimetic absorbent, cellulose acetate (CA) embedded with triolein (CA-triolein), was prepared and applied for the removal of persistent organic pollutants (POPs) from micro-polluted aqueous solution. The comparison of CA-triolein, CA and granular activated carbon (GAC) for dieldrin removal was investigated. Results showed that CA-triolein absorbent gave a lowest residual concentration after 24 h although GAC had high removal rate in the first 4 h adsorption. Then the removal efficiency of mixed POPs (e.g. aldrin, dieldrin, endrin and heptachlor epoxide), absorption isotherm, absorbent regeneration and initial column experiments of CA-triolein were studied in detail. The linear absorption isotherm and the independent absorption in binary isotherm indicated that the selected POPs are mainly absorbed onto CA-triolein absorbent by a partition mechanism. The absorption constant, K, was closely related to the hydrophobic property of the compound. Thermodynamic calculations showed that the absorption was spontaneous, with a high affinity and the absorption was an endothermic reaction. Rinsing with hexane the CA-triolein absorbent can be regenerated after absorption of POPs. No significant decrease in the dieldrin removal efficiency was observed even when the absorption–regeneration process was repeated for five times. The results of initial column experiments showed that the CA-triolein absorbent did not reach the breakthrough point at a breakthrough empty-bed volume (BV) of 3200 when the influent concentration was 1–1.5 μg/L and the empty-bed contact time (EBCT) was 20 min.     

持久性有机污染物在水生食物网中的传递行为

食物网是持久性有机污染物(POPs)在水生生态系统中传递的重要途径,了解其传递行为与机制是POPs生态暴露风险评价的科学基础。从4个方面展开了讨论和分析:(1)食物网主要特征(营养级和食物链长度)与POPs环境行为的关系;(2)POPs在底栖及底栖-浮游耦合食物网中的环境行为;(3)微食物网对POPs环境行为的作用;(4)食物网的变化对POPs环境行为的影响。主要结论如下:(1)已有研究对水生生物中POPs生物放大作用存在较大争议。一般营养级越高,POPs生物富集性越强,但由于各种生态和生理性质的影响,也存在例外情况。食物链长度与POPs生物富集性呈正相关。(2)POPs通过底栖食物网将沉积物中的POPs向上传递,底栖-浮游食物网的耦合提高了高营养级消费者的暴露风险,目前就POPs在底栖食物网中的生物放大性是否大于浮游食物网存在争议。(3)微生物具有较大的比表面积,是吸附POPs的重要载体。另,沉积物中的微生物通过分解有机质,将POPs释放到水柱中。微生物降解也是环境中POPs脱离环境的重要途径。(4)在内、外压力下,食物网结构和功能发生变化,使物质和能量的传递方向和效率发生改变,并与环境理化性质的变化互相耦合,影响POPs的环境行为。当前研究的重点多集中在POPs在浮游食物网,尤其是高营养级浮游食物网中的环境行为,对POPs在底栖及底栖-浮游耦合食物网和微食物网中环境行为的研究相对缺乏。有关POPs在食物网中环境行为的研究多集中在食物网的某个部分,时间尺度较短,缺乏对POPs环境行为动态变化的研究,未来需深入开展多尺度和多角度的POPs在食物网中环境行为的动态变化研究。新型POPs的生产和使用量不断增加,但有关其在食物网中环境行为的相关分析还较为匮乏,需加强研究。     

持久性有机污染物污染及其防治

随着化学工业的快速发展,持久性有机污染物（POPs）的污染愈来愈成为突出的环境问题,对生态和人体健康构成严重威胁。文章从生物学的角度,对POPs的特性、分布和对动物与人体健康的危害等方面作了简要的介绍。对POPs污染与危害,提出了相应的治理措施。     

A review on emerging persistent organic pollutants: Current scenario in Pakistan

During the last few years, a new drift on screening of persistent organic pollutants (POPs) present in the environment of Pakistan has been observed. However, across the globe a number of reports have been devoted to the screening levels, distribution, and risk assessment and on the emission of POPs. In the case of Pakistan, the knowledge achieved and understanding of POPs contamination in the environmental compartments are still limited. Recently published literature has been a key to explore the mystery of new emerging POPs from the environment of the country. In this review, an effort was made to summarize the results of recently published reports on POPs (PCNs, PBDEs, DPs, and PCBs) from biotic and abiotic environments of Pakistan. This review also presents the available data published to date for organochlorines. The results of previously reported studies reflected that newly emerging POPs were influenced by the industrial and urban fractions and were in line with the distribution pattern of other regions of the world. These results revealed that urgent attention must be paid to these new emerging POPs, as they are reported to be present in considerable concentrations. Such detected concentrations of these banned pollutants should be checked/screened by scientific authorities to avoid adverse health risks to humans and animals.     

High-spin binuclear cyclopentadienyliron chlorides: a density functional theory study

Theoretical studies on the cyclopentadienyliron chlorides Cp₂Fe₂Cl _n (n?=?6???1) with iron in the formal oxidation states from +1 to +4 indicate that all the high-spin species are predicted to be the lowest energy structures and they are paramagnetic complexes with magnetic moments between 2.8μ _B and 5.9μ _B. The mixed oxidation state derivatives with odd number of chloride atoms have larger magnetic moments than other species. In addition to Cp₂Fe₂Cl, which has the largest magnetic moment, these high-spin species have terminal Cp rings and bridging Cl atoms up to a maximum of two bridges. The Cp₂Fe₂Cl₄, Cp₂Fe₂Cl₃ and Cp₂Fe₂Cl₂ derivatives are predicted to be thermodynamically stable molecules with respect to exothermic reactions for the loss of one Cl atom from Cp₂Fe₂Cl _n . Moreover, the lowest energy Cp₂Fe₂Cl _n (n?=?3, 4) derivatives can be derived by the oxidative addition reactions of Cp₂Fe₂Cl _n?2 + Cl₂ → Cp₂Fe₂Cl _n .

(Re)Greening photochemistry: using light for degrading persistent organic pollutants

Light is a cheap and abundant chemical reagent, capable of inducing highly selective reactions, some of which cannot be reasonably carried out by alternative ways nowadays. Photochemical processes may take place directly from the excited states or short-lived intermediates generated after light absorption or, alternatively, through reaction with species indirectly generated by the action of light on other chemicals present in the medium (catalysts or secondary reagents). As a consequence a range of possibilities are open to transform and/or degrade refractory pollutants or undesired chemicals or microbia in air, water, soil, on surfaces, etc., as well as other applications described below.     

Exposing culprit organic pollutants: a review

There is a continuing need for monitoring the health of the environment due to the presence of pollutants. Here, we review the development and attributes of biosensors by which bacteria have been genetically modified to express the luminescence genes, i.e. to glow, in a quantified manner, in response to pollutants. We have concentrated on the detection of organic hydrocarbon pollutants and discussed the molecular mechanisms by which some of these chemicals act as effector molecules on the respective regulatory systems. The future of environmental biosensors is predictably bright. As more knowledge is gathered on the sensing regulatory component, the possibility of developing targeted or pollutant-specific biosensors is promising. Moreover, the repertoire of biosensors for culprit organic pollutants is expected to be enlarged through advances in genomics technology and identification of new sensory or receptor molecules. The need for pollutant detection at concentrations in the parts per trillion range or biosensors configured in a nanoscale is anticipated.     

Spectroscopic investigation on glutamic acid by Coulomb-attenuating and double hybrid density functional theory methods

This study deals with the identification of glutamic acid by means of quantum chemical approach. FT-IR, FT-Raman and UV–vis spectra were recorded in the region 4000–400, 4000–50 cm^? 1 and 200–600 nm, respectively. CAM-B3LYP/6-31G(d,p) and B2PLYP/6-31G(d,p) calculations were performed to obtain the optimised molecular structures, vibrational frequencies and corresponding vibrational assignment, thermodynamic properties and natural bonding orbital (NBO) analysis. The results show that the obtained optimised geometric parameters (bond lengths, bond angles and bond dihedrals) and vibrational frequencies were found to be in good agreement with the experimental results. The calculations of the electronic spectra were compared with the experimental ones. Furthermore, highest occupied molecular orbital and lowest unoccupied molecular orbital analyses and UV–vis spectral analysis were also performed to determine the energy band gaps and transition states. NBO analysis, calculated using density functional theory methods (CAM-B3LYP/6-31G(d,p) and B2PLYP/6-31G(d,p)), was induced to find inter-molecular atoms. ¹³C and ¹H NMR isotropic chemical shifts were calculated and the assignments made were compared with the ChemDraw Ultra values.     

An investigation of the pyranose ring interconversion path of alpha-L-idose calculated using density functional theory

The interconversion pathways of the pyranose ring conformation of alpha-L-idose from a (4)C1 chair to other conformations were investigated using density functional calculations. From these calculations, four different ring interconversion paths and their transition state structures from the (4)C1 chair to other conformations, such as B(3,O), and (1)S3, were obtained. These four transition-state conformations cover four possible combinations of the network patterns of the hydroxyl group hydrogen bonds (clockwise and counterclockwise) and the conformations of the primary alcohol group (tg and gg). The optimized conformations, transition states, and their intrinsic reaction coordinates (IRC) were all calculated at the B3LYP/6-31G** level. The energy differences among the structures obtained were evaluated at the B3LYP/6-311++G** level. The optimized conformations indicate that the conformers of (4)C1, (2)S(O), and B(3,O) have similar energies, while (1)S3 has a higher energy than the others. The comparison of the four transition states and their ring interconversion paths, which were confirmed using the IRC calculation, suggests that the most plausible ring interconversion of the alpha-L-idopyranose ring occurs between (4)C1 and B(3,O) through the E3 envelope, which involves a 5.21 kcal/mol energy barrier.     

Hydrogen bonds in galactopyranoside and glucopyranoside: a density functional theory study

Density functional theory calculations on two glycosides, namely, n-octyl-β-D-glucopyranoside (C₈O-β-Glc) and n-octyl-β-D-galactopyranoside (C₈O-β-Gal) were performed for geometry optimization at the B3LYP/6-31G level. Both molecules are stereoisomers (epimers) differing only in the orientation of the hydroxyl group at the C4 position. Thus it is interesting to investigate electronically the effect of the direction (axial/equatorial) of the hydroxyl group at the C4 position. The structure parameters of X-H???Y intramolecular hydrogen bonds were analyzed, while the nature of these bonds and the intramolecular interactions were considered using the atoms in molecules (AIM) approach. Natural bond orbital analysis (NBO) was used to determine bond orders, charge and lone pair electrons on each atom and effective non-bonding interactions. We have also reported electronic energy and dipole moment in gas and solution phases. Further, the electronic properties such as the highest occupied molecular orbital, lowest unoccupied molecular orbital, ionization energy, electron affinity, electronic chemical potential, chemical hardness, softness and electrophilicity index, are also presented here for both C₈O-β-Glc and C₈O-β-Gal. These results show that, while C₈O-β-Glc possess– only one hydrogen bond, C₈O-β-Gal has two intramolecular hydrogen bonds, which further confirms the anomalous stability of the latter in self-assembly phenomena.     

The 5'-deoxyadenylic acid molecule conformational capacity: quantum-mechanical investigation using density functional theory (DFT)

Exhaustive conformational analysis of the 5'-deoxyadenylic acid molecule, has been carried out by the quantum-mechanical density functional theory method at the MP2/6-311++G(d,p)//DFT B3LYP/6-31G(d,p) theory level. As many as 726 of its conformations have been revealed with the relative gas phase Gibbs energies under standard conditions from 0 to 12.1 kcal/mole. It has been shown, that the energetically most favorable conformation has north sugar puckering and synorientation of the nitrogenous base and is stabilized by intramolecular O(p1)H(p1)-N3 and O3'H-O(p) hydrogen bonds. Four conformations have been shown to have their geometry similar to that of AI-DNA and four - of BI-DNA. One conformer of the 5'-deoxyadenylic acid molecule is similar to its sodium salt hexahydrate structure in crystalline state resolved by the X-ray diffraction method and taken from literature. It is shown that effective charges of C4' and C5' atoms are the most sensitive to the molecule conformation ones. The role of the intramolecular OH-N hydrogen bonds in formation of the 5'-deoxyadenylic acid molecule structure has been demonstrated.     

Structure and spectral characteristics of diquat-cucurbituril complexes from density functional theory

Electronic structure, ¹H NMR and infrared spectra of diquat (6,7-dihydrodipyrido[1,2-b:1′,2′-e] pyrazine-5,8-diium or DQ²⁺) encapsulated by cucurbit[n]uril (n?=?7,8) hosts are obtained using the density functional theory. Theoretical calculations have shown that both CB[7] or CB[8] host possesses strong affinity toward DQ²⁺ compared to its reduced cation or neutral species. Calculated ¹H NMR spectra reveal that H_α protons on bi-pyridinium rings of DQ²⁺@CB[8] complex are de-shielded owing to C=O?H interactions. On the other hand aromatic (H_β and H_δ) of DQ²⁺ within the CB[8] cavity exhibit significant shielding. The complexation of CB[8] with DQ²⁺ splits the carbonyl stretching vibration (1788 cm^?1) into two distinct vibrations which correspond to 1765 cm^?1 arising from hydrogen bonded carbonyls and the 1792 cm^?1 band from non-interacting ones. Further, the CN stretching vibration in DQ²⁺ exhibits a frequency blue-shift of 6 cm^?1 on its encapsulation within the CB[8] cavity. The direction of frequency shift has been explained on the basis of natural bond orbital analyses.

Natural polyprenylated benzophenone: keto-enol tautomerism from density functional calculations and the AIM theory

The quantum theory of atoms in molecules (QTAIM) and density functional theory (DFT) calculations were employed to investigate the structure and tautomeric equilibrium of epiclusianone, a polyisoprenylated benzophenone with interesting biological activities. Two different exchange-correlation functionals were employed, namely ωB97x-D and M06-2x, including implicit solvent models (benzene and DMSO). Our results for the thermodynamic properties show that the isomer in which the H atom is bonded to the oxygen away from the benzene ring is the most stable tautomer form of the epiclusianone, thus confirming previous charge density analysis from X-ray diffraction data (Martins et al. J Braz Chem Soc 18(8):1515–1523, 22).