溴系阻燃剂在环境及人体中的存在和代谢转化

溴系阻燃剂的广泛使用及其对环境和人体的危害,受到人们的广泛关注。本文简要介绍了在环境与生态系统及人体中存在的三种主要溴系阻燃剂：多溴联苯醚、六溴环十二烷和四溴双酚A,重点评述了它们在环境介质（污水、淤泥及沉积物）、生物体（微生物及动物）、人体中及光热作用下的代谢与转化,并详细介绍了其代谢途径及代谢产物。     

环境中多溴联苯醚类(PBDEs)化合物污染研究

由于环境中PBDEs的浓度在快速增长且已在世界各地普遍存在,又因PBDEs的化学结构与PCB和DDT非常相似,因此PBDEs的环境毒性越来越多地受到学者们的关注。本文介绍PBDEs在环境介质中如水介质（河流、海洋、废水和沉积物）,野生动物（海洋哺乳动物、鱼）和人体组织内（母乳、血清、脂肪）的分布及其毒性效应和对人类健康的威胁,着重介绍美国所进行的两个研究实例,也介绍了有关国家对PBDEs采取的预防和控制措施。     

Spectro-Microscopic Techniques for Studying Nanoplastics in the Environment and in Organisms

Nanoplastics (NPs), small (<1 μm) polymer particles formed from bulk plastics, are a potential threat to human health and the environment. Orders of magnitude smaller than microplastics (MPs), they might behave differently due to their larger surface area and small size, which allows them to diffuse through organic barriers. However, detecting NPs in the environment and organic matrices has proven to be difficult, as their chemical nature is similar to these matrices. Furthermore, as their size is smaller than the (spatial) detection limit of common analytical tools, they are hard to find and quantify. We highlight different micro-spectroscopic techniques utilized for NP detection and argue that an analysis procedure should involve both particle imaging and correlative or direct chemical characterization of the same particles or samples. Finally, we highlight methods that can do both simultaneously, but with the downside that large particle numbers and statistics cannot be obtained.     

Progress in the analytical research methods of polycyclic aromatic hydrocarbons (PAHs)

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are one species of persistent organic pollutants (POPs) with strong carcinogenicity and teratogenicity. They can be widely found in the environment, which cause great harm to the ecological environment. In addition, they endanger human health by polluting food from the natural environment and food processing. Therefore, it is necessary to accurately detect PAHs in various sample matrices, which requires the accurate, practical and rapid detection methods. This review aims to investigate the progress of research methods for PAHs, including pretreatment methods and detection methods. A summary analysis of different methods is performed by searching the literature on numerous methods for detecting PAHs published in various journals. There are many pretreatment methods for PAHs, such as solid phase extraction (SPE), cloud point extraction (CPE) and so on. The most commonly used methods for detecting PAHs are high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS). Spectrophotometry, chromatography and chromatography-mass spectrometry have been used more frequently owing to their accuracy and convenience. At the same time, some immunological methods, such as immunosensormethods, enzyme-linked immunosorbent assays (ELISA), immunofluorescence, etc. are also widely used.     

Analytical methods for the assessment of endocrine disrupting chemical exposure during human fetal and lactation stages: A review

In the present work, a review of the analytical methods developed in the last 15 years for the determination of endocrine disrupting chemicals (EDCs) in human samples related with children, including placenta, cord blood, amniotic fluid, maternal blood, maternal urine and breast milk, is proposed. Children are highly vulnerable to toxic chemicals in the environment. Among these environmental contaminants to which children are at risk of exposure are EDCs —substances able to alter the normal hormone function of wildlife and humans—. The work focuses mainly on sample preparation and instrumental techniques used for the detection and quantification of the analytes. The sample preparation techniques include, not only liquid–liquid extraction (LLE) and solid-phase extraction (SPE), but also modern microextraction techniques such as extraction with molecular imprinted polymers (MIPs), stir-bar sorptive extraction (SBSE), hollow-fiber liquid-phase microextraction (HF-LPME), dispersive liquid–liquid microextraction (DLLME), matrix solid phase dispersion (MSPD) or ultrasound-assisted extraction (UAE), which are becoming alternatives in the analysis of human samples. Most studies focus on minimizing the number of steps and using the lowest solvent amounts in the sample treatment. The usual instrumental techniques employed include liquid chromatography (LC), gas chromatography (GC) mainly coupled to tandem mass spectrometry. Multiresidue methods are being developed for the determination of several families of EDCs with one extraction step and limited sample preparation.     

基于适配体技术的雌性激素检测方法研究进展

雌激素是一种类固醇激素,属于环境内分泌干扰物,可在人体和动物体内积累并起到类似雌激素的作用,使生物体的内分泌失衡,因此开发简单快速灵敏的雌激素检测方法具有重要意义。核酸适配体是通过指数富集配体系统进化技术(SELEX)筛选得到的一条寡核苷酸序列,能够与靶标高亲和力特异性结合,与传统抗体相比,具有靶标范围广、易合成修饰、稳定性高等特点,因而被广泛用于分析检测领域。该文主要综述了雌激素适配体的筛选进展以及适配体技术在雌激素检测中的应用,并对核酸适配体技术在雌激素检测领域的应用前景进行了展望。     

Preparation, characterization and in vitro anticancer activity of platinum(II) complexes with N-Cyclohexyl-1,3-propanediamine as the carrier

New JM118 (active form of satraplatin) analogues with N-cyclohexyl-1,3-propanediamine (N-chpda) as the carrier, cis-[Pt(N-chpda)X2] (X2=2Cl(-) (1), oxalate (2), malonate (3), 1,1-cyclobutanedicarboxylate (CBDCA) (3), and 3-hydroxy-1,1-cyclobutanedicarboxylate(HO-CBDCA) (4)), have been synthesized and characterized by elemental analysis and spectroscopic data along with X-ray crystal structure for a representative compound cis-[Pt(N-chpda)Cl2]. The complexes have also been evaluated for their in vitro anticancer activity. All these analytical data are in good agreement with the structures of the desired compounds. The Pt(II) is in a square planar environment and is coordinated by a chelating N-chpda ligand and 2Cl(-) in cis position, and there are two crystallographically independent cis-[Pt(N-chpda)Cl2] molecules linked together by intermolecular N-H...Cl hydrogen bonds. Compounds 1 and 2 are very active against human lung cancer cell line (AGZY) and human lymphocytic leukemia cell line (Raji), and are much more active than carboplatin. Platinum(II) complexes with N-cyclohexyl-1,3-propanediamine is an alternative choice for mixed ammine/aminoplatinum anticancer drugs.     

Identifying and localizing intracellular nanoparticles using Raman spectroscopy

Raman microscopy is employed to spectroscopically image biological cells previously exposed to fluorescently labelled polystyrene nanoparticles and, in combination with K-means clustering and principal component analysis (PCA), is demonstrated to be capable of localising the nanoparticles and identifying the subcellular environment based on the molecular spectroscopic signatures. The neutral nanoparticles of 50 nm or 100 nm, as characterised by dynamic light scattering, are shown to be non-toxic to a human lung adenocarcinoma cell-line (A549), according to a range of cytotoxicity assays including Neutral Red, Alamar Blue, Coomassie Blue and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT). Confocal fluorescence microscopy identifies intracellular fluorescence due to the nanoparticle exposure, but the fluorescence distribution is spatially diffuse, potentially due to detachment of the dye from the nanoparticles, and the technique fails to unambiguously identify the distribution of the nanoparticles within the cells. Raman spectroscopic mapping of the cells in combination with K-means cluster analysis is used to clearly identify and localise the polystyrene nanoparticles in exposed cells, based on their characteristic spectroscopic signatures. PCA identifies the local environment as rich in lipidic signatures which are associated with localisation of the nanoparticles in the endoplasmic reticulum. The importance of optimised cell growth conditions and fixation processes is highlighted. The preliminary study demonstrates the potential of the technique to unambiguously identify and locate nonfluorescent nanoparticles in cells and to probe not only the local environment but also changes in the cell metabolism which may be associated with cytotoxic responses.     

Remove of Heavy Metals(Cu2+, Pb2+, Zn2+ and Cd2+) in Water Through Modified Diatomite

At present, heavy metal pollution has become a major environmental problem, influencing the survival of human and other creatures. Developing heavy metal ion adsorbents, which are environment friendly, of low cost and good performance is one of the effective means to solve heavy metal pollution. Rich low-grade diatomite mineral, as raw material, was modified with calcium carbonate to improve the adsorption properties of diatomite for heavy metal ions. The effects of dosage(m), pH, adsorbing time(t), temperature(T) and concentration of adsorbent(c) on the removal rate of heavy metal ions(Cu²⁺, Pb²⁺, Zn²⁺ and Cd²⁺) were studied. The results show that under the suitable conditions, T=15 ℃, c=1.5 mmol/L, m=10 g/L, t=60 min, in a weak acid environment, the removal effect of the four kinds of metal ions by modified diatomite is the best.     

镉毒性毒理学研究进展

镉是目前最常见的一种重金属环境污染物,并且危害性极大。综述了镉毒性毒理学研究进展,包括：镉对生殖、骨骼、肾脏、神经等系统或组织的毒性和致毒机理研究。     

Microplastics in Mediterranean coastal area: toxicity and impact for the environment and human health

The so-called marine litter, and in particular microplastics (MPs) and nanoplastics (NPs), are ubiquitously distributed and recognised as an emerging risk for the environment and human health. It is known that marine environments are one of the most impacted areas and among them; coastal zones are the most contaminated ones. They are subjected to population pressure, tourism, harbours, desalination plants, marine traffic and fish farms.This review is focused on the Mediterranean Sea, currently considered one hot spot of microplastics pollution in the world, as a consequence of the high number of plastic marine litter generating activities and its characteristic morphology of semi-enclosed sea. MPs and NPs have been detected not only in surface water and water columns but also in sediments, deep seafloor, and biota including fish and seafood for human consumption. Because of this, different European legislation initiatives have been launched during the last years in order to prevent MPs and NPs contamination and to face derived problems. Finally, this review summarises the main problems and shortcomings associated to MPs and NPs analyses such as their identification and quantification or the necessity of standardised protocols.     

Advances in the study of current-use non-PBDE brominated flame retardants and dechlorane plus in the environment and humans

The fate of the high production volume,currently in use,and not regulated non-polybrominated diphenyl ether(PBDE) flame retardants,such as tetrabromobisphenol A(TBBPA) ,hexabromocyclododecane(HBCD) and dechlorane plus(DP),and the alternative flame retardants of PBDE,such as BTBPE and DBDPE,in the environment has attracted increasing attention and aroused concern due to the increasing regulation and phasing-out of PBDEs.This paper reviews the distribution,bioaccumulation,human exposure and environmental beha...     

Isolation of Stable Mutagenic Photodecomposition Products of Benzo(a)pyrene by Thin-Layer Chromatography

Abstract

Polycyclic aromatic hydrocarbons (PAH) are widespread in the atmosphere, the soil, waterways and oceans, as well as in the food chain. Major sources of PAH include emissions from transportation systems, heat and power generating plants, refuse burning and industrial processes (1,2,3). A significant number of these PAH are known to be carcinogenic (2,4,5). Epidemiological studies indicate that the environment is a significant factor in the incidence of human cancer, although many of the specific causal agents remain to be identified. One widely studied PAH i s benzo(a)pyrene (BaP), which is a carcinogen, and one of the most common PAH contaminants of the environment (6). Occupational exposure t o BaP has been documented (4). Mailath and Morik (7) studied the effect of sunlight and dark-room storage on BaP and reported that six and eight compounds, respectively, were observed when BaP was exposed to sunlight or left in the dark. There have been several reports of the degradation of BaP adsorbed on soot or smoke particles (8,9,10).     

近海环境中抗生素分析样品前处理技术的研究进展

抗生素在人和动物疾病防治方面的广泛及大量使用造成其源源不断地进入到环境中,并最终通过各种途径进入到近海环境中。由于抗生素可在水生生物体内蓄积,特别是其可促进细菌耐药性的产生与传播,已经威胁到生态和人类健康。抗生素种类复杂、性质各异,且在环境中存在浓度低,因此,发展各种基质中抗生素分析的前处理方法至关重要。该文综述了近十几年来近海水体、沉积物和生物体中抗生素的前处理方法,主要包括固相萃取、固液萃取、基质固相分散萃取和QuEChERS等几种常用前处理技术,并对方法中可能影响萃取和净化效果的各种因素进行了分析,最后对各种方法的优缺点和发展进行了总结和展望。     

Shining Light on Skin Pigmentation: The Darker and the Brighter Side of Effects of UV Radiation(†)

The term barrier function as applied to human skin often connotes the physical properties of this organ that provides protection from its surrounding environment. This term does not generally include skin pigmentation. However, skin pigmentation, which is the result of melanin produced in melanocytes residing in the basal layer of the skin and exported to the keratinocytes in the upper layers, serves equally important protective function. Indeed, changes in skin pigmentation are often the most readily recognized indicators of exposure of skin to damaging agents, especially to natural and artificial radiation in the environment. Several recent studies have shed new light on (1) the mechanisms involved in selective effects of subcomponents of UV radiation on human skin pigmentation and (2) the interactive influences between keratinocytes and melanocytes, acting as "epidermal melanin unit," that manifest as changes in skin pigmentation in response to exposure to various forms of radiation. This article provides a concise review of our current understanding of the effects of the nonionizing solar radiation, at cellular and molecular levels, on human skin pigmentation.     

Synthesis and characterization of azolate gold(I) phosphane complexes as thioredoxin reductase inhibiting antitumor agents

Following an increasing interest in the gold drug therapy field, nine new neutral azolate gold(I) phosphane compounds have been synthesized and tested as anticancer agents. The azolate ligands used in this study are pyrazolates and imidazolates substituted with deactivating groups such as trifluoromethyl, nitro or chloride moieties, whereas the phosphane co-ligand is the triphenylphosphane or the more hydrophilic TPA (TPA = 1,3,5-triazaphosphaadamantane). The studied gold(I) complexes are: (3,5-bis-trifluoromethyl-1H-pyrazolate-1-yl)-triphenylphosphane-gold(I) (1), (3,5-dinitro-1H-pyrazolate-1-yl)-triphenylphosphane-gold(I) (2), (4-nitro-1H-pyrazolate-1-yl)-triphenylphosphane-gold(I) (5), (4,5-dichloro-1H-imidazolate-1-yl)-triphenylphosphane-gold(I) (7), with the related TPA complexes (3), (4), (6) and (8) and (1-benzyl-4,5-di-chloro-2H-imidazolate-2-yl)-triphenylphosphane-gold(I) (9). The presence of deactivating groups on the azole rings improves the solubility of these complexes in polar media. Compounds 1-8 contain the N-Au-P environment, whilst compound 9 is the only one to contain a C-Au-P environment. Crystal structures for compounds 1 and 2 have been obtained and discussed. Interestingly, the newly synthesized gold(I) compounds were found to possess a pronounced cytotoxic activity on several human cancer cells, some of which were endowed with cis-platin or multidrug resistance. In particular, among azolate gold(I) complexes, 1 and 2 proved to be the most promising derivatives eliciting an antiproliferative effect up to 70 times higher than cis-platin. Mechanistic experiments indicated that the inhibition of thioredoxin reductase (TrxR) might be involved in the pharmacodynamic behavior of these gold species.     

环境水样及固相样品中全氟化合物分析方法研究进展

全氟化合物(Perfluorinated compounds,PFCs)是一类持久性有机污染物,在环境中普遍检出,严重危害人体健康,已成为环境科学和毒理学研究的热点之一.PFCs含有较多同系物及同分异构体,且在环境中通常为痕量水平(ng/g或μg/L),迫切需要建立灵敏可靠的样品前处理和检测技术.国内外已针对环境样品基质中痕量PFCs的检测开展了大量研究,但有关复杂环境样品中PFCs前处理方法、分析方法、基质效应等方面的系统评述还相对较少.本文综述了环境样品(水、沉积物/污泥、土壤、植物)中PFCs的前处理方法、检测方法(尤其是同分异构体)及环境样品基质效应对其检测的影响,以期为相关研究提供参考.     

Human telomeric DNA forms parallel-stranded intramolecular G-quadruplex in K+ solution under molecular crowding condition

The G-rich strand of human telomeric DNA can fold into a four-stranded structure called G-quadruplex and inhibit telomerase activity that is expressed in 85-90% tumor cells. For this reason, telomere quadruplex is emerging as a potential therapeutic target for cancer. Information on the structure of the quadruplex in the physiological environment is important for structure-based drug design targeting the quadruplex. Recent studies have raised significant controversy regarding the exact structure of the quadruplex formed by human telomeric DNA in a physiological relevant environment. Studies on the crystal prepared in K+ solution revealed a distinct propeller-shaped parallel-stranded conformation. However, many later works failed to confirm such structure in physiological K+ solution but rather led to the identification of a different hybrid-type mixed parallel/antiparallel quadruplex. Here we demonstrate that human telomere DNA adopts a parallel-stranded conformation in physiological K+ solution under molecular crowding conditions created by PEG. At the concentration of 40% (w/v), PEG induced complete structural conversion to a parallel-stranded G-quadruplex. We also show that the quadruplex formed under such a condition has unusual stability and significant negative impact on telomerase processivity. Since the environment inside cells is molecularly crowded, our results obtained under the cell mimicking condition suggest that the parallel-stranded quadruplex may be the more favored structure under physiological conditions, and drug design targeting the human telomeric quadruplex should take this into consideration.     

Analysis of industrial contaminants in indoor air: Part 1. Volatile organic compounds,carbonyl compounds,polycyclic aromatic hydrocarbons and polychlorinated biphenyls

This article reviews recent literature on the analysis of industrial contaminants in indoor air in the framework of the REACH project, which is mainly intended to improve protection of human health and the environment from the risks of more than 34 millions of chemical substances. Industrial pollutants that can be found in indoor air may be of very different types and origin, belonging to the volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) categories. Several compounds have been classified into the priority organic pollutants (POPs) class such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and furans (PCDD/PCDFs) and related polychlorinated compounds, and polycyclic aromatic hydrocarbons (PAHs). Many of these compounds are partially associated to the air gas phase, but also to the suspended particulate matter. Furthermore, settled dust can act as a concentrator for the less volatile pollutants and has become a matrix of great concern for indoors contamination. Main literature considered in this review are papers from the last 10 years reporting analytical developments and applications regarding VOCs, aldehydes and other carbonyls, PCBs, PCDDs, PCDFs, and PAHs in the indoor environment. Sample collection and pretreatment, analyte extraction, clean-up procedures, determination techniques, performance results, as well as compound concentrations in indoor samples, are summarized and discussed. Emergent contaminants and pesticides related to the industrial development that can be found in indoor air are reviewed in a second part in this volume.     

Determination of steroid hormones in biological and environmental samples using green microextraction techniques: an overview

Residues of steroid hormones have become a cause for concern because they can affect the biological activity of non-target organisms. Steroid hormones are a potential risk for wildlife and humans through the consumption of contaminated food or water. Their determination requires extraction and clean-up steps, prior to detection, to reach low concentration levels. In recent years, a great effort has been made to develop new analytical methodologies, such as microextraction techniques, that reduce environmental pollution. Researchers have modified old methods to incorporate procedures that use less-hazardous chemicals or that use smaller amounts of them. They are able to do direct analysis using miniaturised equipment and reduced amounts of solvents and wastes. These accomplishments are the main objectives of green analytical chemistry. In this overview, we focus on microextraction techniques for the determination of steroid hormones in biological (e.g., human urine, human serum, fish, shrimp and prawn tissue and milk) and environmental (e.g., wastewaters, surface waters, tap waters, river waters, sewage sludges, marine sediments and river sediments) samples. We comment on the most recent applications in sorptive-microextraction modes, such as solid phase microextraction (SPME) with molecularly imprinted polymers (MIPs), in-tube solid-phase microextraction (IT-SPME), stir-bar sorptive extraction (SBSE) and microextraction in packed sorbent (MEPS). We also describe liquid-phase microextraction (LPME) approaches reported in the literature that are applied to the determination of steroid hormones.