Poly[β-(1→4)-2-amino-2-deoxy-D-glucopyranose] based zero valent nickel nanocomposite for efficient reduction of nitrate in water

Chemical reduction of nitrate using metal nanoparticles has received increasing interest due to over-dependence on groundwater and consequence health hazard of the nitrate ion. One major drawback of this technique is the agglomeration of nanoparticles leading to the formation of large flocs. A low cost biopolymeric material, poly [β-(1 → 4)-2-amino-2-deoxy-D-glucopyranose] (β-PADG) obtained from deacetylated chitin was used as stabilizer to synthesize zero valent nickel (ZVNi) nanoparticles. The β-PADG-ZVNi nanocomposite was characterized using infra red (IR), UV-Vis spectrophotometric techniques and Scanning Electron Microscope (SEM). The morphology of the composite showed that β-PADG stabilized-ZVNi nanoparticles were present as discrete particles. The mean particle size was estimated to be (7.76 ± 2.98) nm and surface area of 87.10 m²/g. The stabilized-ZVNi nanoparticles exhibited markedly greater reactivity for reduction of nitrate in water with 100% conversion within 2 hr contact owing to less agglomeration. Varying the β-PADG-to-ZVNi ratio and the ZVNi-to-nitrate molar ratio generally led to a faster nitrate reduction. About 3.4-fold difference in the specific reaction rate constant suggests that the application of the β-PADG-stabilizer not only increased the specific surface area of the resultant nanoparticles, but also greatly enhanced the surface reactivity of the nanoparticles per unit area.     

白腐菌锰过氧化物酶对2,2’,4,4’-四溴联苯醚的降解

多溴联苯醚(PBDEs)是一类在环境中普遍存在的全球性有机污染物,对这类污染物环境行为的研究虽然已有较多报道,但是微生物降解方面尤其是针对单一胞外酶降解的研究还比较少。文章以白腐菌模式菌种Phanerochaete chrysosporium为对象,研究其分泌的胞外酶锰过氧化物酶(MnP)对环境中最常检测到的2,2’,4,4’-四溴联苯醚(BDE47)的好氧降解,考察不同β-环糊精浓度对该酶降解BDE47的影响,并初步探讨了胞内细胞色素P450的作用。结果表明,MnP能有效降解BDE47,在培养15 d后,扣除空白损失,降解率达到70%左右。低浓度和高浓度的环糊精对MnP降解BDE47无显著性影响。胞内细胞色素P450对BDE47的降解没有明显贡献。     

草甘膦对青鳉鱼卵黄蛋白原的诱导及其潜在分子机理

为了研究草甘膦潜在的雌激素效应,将1~3d的雌雄青鳉幼鱼暴露于不同浓度 (0.2, 2, 20, 200, 2000μg/L)的草甘膦5周,发现雌雄鱼肝脏卵黄蛋白原(VTG I)基因表达分别在0.2, 2, 20μg/L浓度(雌鱼)和2, 20, 200μg/L浓度(雄鱼)下受到显著诱导,但在高浓度下(雌鱼,200μg/L和2000μg/L;雄鱼,2000μg/L)恢复到正常水平.草甘膦诱导雌激素效应的机理存在雌雄差异:雌鱼中雌激素效应主要由于草甘膦诱导了脑部FSH和性腺CYP19A基因,从而增加了雌激素合成能力.雄鱼中主要由于草甘膦抑制肝脏中雌激素代谢酶 (CYP1A、CYP1B和CYP3A)而显示雌激素效应.     

Pulmonary inflammation induced by office dust and the relation to 1 → 3-β-glucan using different extraction techniques

It is observed that 1?→?3-β-glucan, a major cell wall component of fungi, induces pulmonary inflammation. There is inconsistency in determining the correlation between the levels of glucan measured by current extraction methods and the respiratory inflammation observed in individuals or lab animals exposed to environmental dust samples. The glucan-specific limulus amebocyte lysate (G-LAL) method was used after extraction with dimethyl sulfoxide (DMSO) or sodium hydroxide (NaOH) to analyze the glucan content of office dust samples collected from a water-damaged building. C3HeB/FeJ mice, an endotoxin-sensitive strain, were treated with different dust samples (2.5?mg?kg^?1 body weight) or saline (vehicle control) by pharyngeal aspiration. At 1?day after aspiration, bronchoalveolar lavage (BAL) was performed, and lung inflammation and injury were assessed by measuring: (1) neutrophil (PMN) infiltration, (2) inflammatory cytokine (IL-6, IL-10, MCP-1, IFN-γ, TNF-α, and IL12-p70) levels, and (3) albumin and lactate dehydrogenase in recovered BAL fluid. Both DMSO and NaOH extraction increased the detection of glucan by approximately 20-fold compared to water extraction. However, only the DMSO extraction method showed a statistically significant positive correlation between 1?→?3-β-glucan and albumin levels, total numbers of BAL, polymorphonuclear leukocytes (PMNs) cells recovered, levels of TNF-α, MCP-1, and IL-6. In conclusion, 1?→?3-β-glucan is a potent inflammatory agent in dust samples and DMSO extraction for glucan analysis may prove useful in understanding the impact of environmental contamination by glucans on lung disease.     

Effects of hydroxypropyl-β-cyclodextrin on pyrene and benzo[α]pyrene: bioavailability and degradation in sotil

Effect of hydroxypropyl-β-cyclodextrin (HPCD) on the bioavailability and biodegradation of the polycyclic aromatic hydrocarbons (PAHs) pyrene (PYR) and benzo[α]pyrene (BaP) in spiked soils was investigated in 14-week incubation experiments. To evaluate the effect of HPCD in soils with a different matrix, humic substance (HS) was added into soil samples. A 6-h Tenax TA extraction method was used to evaluate pollutants bioavailability. The biodegraded and extracted fractions were compared to evaluate the impact of HPCD on PAHs biodegradation. Results indicated positive effects of HPCD on fast desorption behaviours of PAHs. The biodegraded fraction was consistent with that of the extracted for PYR. However, in terms of BaP, the results were contrary which suggests that biological factors may be limiting factors for BaP pollution remediation. HS weakened the HPCD solubilisation effect while accelerated the decay of PYR and BaP, also implying that bioavailability was not the sole factor limiting PAH biodegradation. In addition, analysis of microbial communities demonstrated that HPCD inhibited the growth of some soil bacteria while HS promoted the evolution of some soil microorganisms. A limited population of hydrocarbon degrader populations led to observing incomplete PAH biodegradation even in the presence of HPCD.     

集约化养猪废水SBR中17β-雌二醇高效降解菌的分离鉴定及其降解特性

从集约化养猪废水生物处理SBR的活性污泥中分离到3株高效降解17β-雌二醇(E2)的菌株,分别命名为ha、chs和hc。研究表明,这3株菌以E2为惟一碳源,在4 d内对初始浓度为1 mg/L E2的降解率为70%～95%。25℃条件下菌ha、chs和hc的一级反应动力学常数分别为0.0086、0.072和0.013。在温度为37℃时,3株菌的降解效率最高,在高浓度的氨氮和碱性pH的条件下,这3株菌均存在降解作用。其中,pH 9.05时,一级动力学常数菌ha降至0.0066,菌chs升至0.076,菌hc降至0.012。同时,在添加C源后,对降解有促进作用,并且C/N比在15∶1时降解效果较好。3株菌的一级反应动力学常数分别升到0.027、0.73和0.021。经16S rRNA基因序列分析鉴定为枯草芽孢肝菌(Bacillus subtilis)。     

Degradation of 17α-ethinylestradiol by ozonation--identification of the by-products and assessment of their estrogenicity and toxicity

The presence of the synthetic estrogen 17α-ethinylestradiol (EE2) in waters at low levels is a concern due to its ability to act as an endocrine disruptor. Ozone (O₃) is commonly used in water treatment and reacts with EE2 to form by-products having characteristics that are mostly unknown. The aim of this study was to identify the by-products of E2 and EE2 ozonation and determine their estrogenicity and toxicity relative to the parent compound. Ozonation by-products were identified via LC-MS analysis. The estrogenicity was measured using the YES assay, and toxicity was determined by monitoring effects on histology of fetal rat testes and testosterone secretion by these tissues. Two EE2 by-products were identified with open phenolic ring structures (masses 302 and 344 u). The Yeast Estrogen Screening (YES) assay showed a decreased but incomplete removal of estrogenicity after ozonation of EE2. Histological analysis of fetal testes revealed that neither E2 nor EE2, with or without ozonation, had any effect on seminiferous cord formation; however, a remarkable negative effect on testosterone secretion was observed, with EE2 by-products after ozonation showing the most rapid and extensive inhibition. These results show that the removal of EE2 via reaction with O₃ resulted in the formation of by-products that are less estrogenic (as demonstrated by the YES assay), but have a greater negative impact on testosterone secretion. Thus, the disappearance of the parent compound is not a sufficient endpoint, as the by-products created may be more toxic. Care should be taken when implementing oxidation applications such as ozone during waste water treatment.     

Dissipation,half-lives,and mass spectrometric identification of endosulfan isomers and the sulfate metabolite on three field-grown vegetables

Endosulfan 3 EC, a mixture of α- and β-stereo isomers, was sprayed on field-grown pepper, melon, and sweet potato plants at the recommended rate of 0.44 kg A.I. acre^?1. Plant tissue samples (leaves, fruits, or edible roots) were collected 1 h to 30 days following spraying and analyzed for endosulfan isomers (α- and β-isomers). Analysis of samples was accomplished using a gas chromatograph (GC) equipped with a mass detector in total ion mode. The results indicated the formation of endosulfan sulfate as the major metabolite of endosulfan sulfite and the relatively higher persistence of the β-isomers as compared to the α-isomer. The initial total residues (α- and β-isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper and melon fruits, the α-isomer, which is the more toxic to mammals, dissipated faster (T_1/2 = 1.22 and 0.95 d, respectively) than the less toxic β-isomer (T_1/2 = 3.0 and 2.5 d, respectively). These results confirm the greater loss of the α-isomer compared to the β-isomer, which can ultimately impact endosulfan dissipation in the environment. Additionally, the higher initial residues of endosulfan on pepper and sweet potato leaves should be considered of great importance for timing field operations and the safe entry of harvesters due to the high mammalian toxicity of endosulfan.     

Host-guest complexes of phenoxy alkyl acid herbicides and cyclodextrins. MCPA and β-cyclodextrin

The chlorophenoxy herbicide MCPA (4-chloro-2-methylphenoxyacetic acid), widely used for the control of broad-leaf weeds primarily in cereal and grass seed crops, still remains one of the most often used herbicides in Portugal. As the formation of inclusion complexes with cyclodextrins can improve its solubility properties, the interaction between the herbicide MCPA and β-cyclodextrin was investigated. The stability constants describing the extent of formation of the complexes have been determined by phase-solubility studies. Different analytical techniques [ultraviolet-visible spectroscopy (UV-Vis), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (¹H NMR)] were employed for a thorough investigation of the structural characteristics of the obtained complexes, which exhibited distinct features and properties from both “guest” and “host” molecules. FTIR and ¹H NMR data obtained for the MCPA/β-CD complexes gave information about the interaction between MCPA and the nonpolar cyclodextrin cavity. The dramatic change observed in band frequency and proton displacements of OCH₂ group and H6 aromatic proton confirmed the inclusion of MCPA in β-CD.

The formation of an inclusion complex between MCPA and β-CD increased the aqueous solubility of this herbicide which could be a particularly advantageous property for some specific applications, namely to improve commercial formulation and for environmental protection.     

Bio-efficacy evaluation of nanoformulations of β-cyfluthrin against Callosobruchus maculatus (Coleoptera: Bruchidae)

In the present investigation, bioefficacy of developed β-cyfluthrin formulations, utilizing laboratory synthesized poly(ethylene glycols) based amphiphilic copolymers, were evaluated against Callosobruchus maculatus (Coleoptera: Bruchidae). The bioefficacy data indicated that the formulations developed by utilizing polymers having PEG – 1500 (3c) and PEG – 2000 (3d) as the hydrophilic segment showed greater efficacy after 14 days as evident from EC₅₀ values (2.2 and 1.58 mg L^?1 respectively). Also, release from the commercial SC formulation was faster than developed formulations as the commercial formulation had the lowest EC₅₀ value on the first day (0.51 mg L^?1). The mean EC₅₀ of the commercial formulation against C. maculatus was quite high as compared to those of developed formulations. The results suggest that depending upon the polymer matrix used, the application rate of β-cyfluthrin can be optimized to achieve insect control at the desired level and period. The results described in this paper are promising and provide a comparison of developed formulations with the commercial one showing an earlier degradation of β-cyfluthrin in the latter and relatively prolonged activity in the former.