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1.
The enantioselective bioactivity against pathogens (Cercospora arachidicola, Fulvia fulva, and Phytophthora infestans) and acute toxicity to Daphnia magna of the fungicide myclobutanil enantiomers were studied. The (+)‐enantiomer in an antimicrobial activity test was about 1.79–1.96 times more active than the (–)‐enantiomer. In the toxicity assay, the calculated 24‐h LC50 values of the (–)‐form, rac‐form and (+)‐form were 16.88, 13.17, and 11.91 mg/L, and the 48‐h LC50 values were 10.15, 9.24, and 5.48 mg/L, respectively, showing that (+)‐myclobutanil was more toxic. Meanwhile, the enantioselective metabolism of myclobutanil enantiomers following a single intravenous (i.v.) administration was investigated in rabbits. Total plasma clearance value (CL) of the (+)‐enantiomer was 1.68‐fold higher than its antipode. Significant differences in pharmacokinetics parameters between the two enantiomers indicated that the high bioactive (+)‐enantiomer was preferentially metabolized and eliminated in plasma. Consistent consequences were found in the tissues (liver, brain, heart, kidney, fat, and muscle), resulting in a relative enrichment of the low‐activity (–)‐myclobutanil. These systemic assessments of the stereoisomers of myclobutanil cannot be used only to investigate environmental and biological behavior, but also have human health implications because of the long persistence of triazole fungicide and enantiomeric enrichment in mammals and humans. Chirality 26:784–789, 2014. © 2014 Wiley Periodicals, Inc.  相似文献   

2.
The bioaccumulation and excretion of enantiomers of myclobutanil in Tenebrio molitor larvae through dietary exposure under laboratory conditions were investigated using high‐performance liquid chromatography tandem mass spectrometry (HPLC‐MS/MS) based on a ChiralcelOD‐3R [cellulosetris‐tris‐(3, 5‐dichlorophenyl‐carbamate)] column. The wheat bran fed to Tenebrio molitor larvae was spiked with racemic myclobutanil at two dose levels of 20 mg/kg and 2 mg/kg (dry weight). The results showed that there was a significant trend of enantioselective bioaccumulation in the larvae with a preferential accumulation of (?)‐myclobutanil in 20 mg/kg dose exposure, but it was not obviously observed in the 2 mg/kg dose group. A kinetic model considering enantiomerization between the two enantiomers based on first‐order reactions was built and the rate constants were estimated to discuss the kinetic reason for the different concentrations of individual enantiomers in the larvae. The approximations implied an inversion between the two enantiomers with a relatively higher rate of the inversion from (?)‐myclobutanil to (+)‐myclobutanil. Meanwhile, analysis of data of excretion samples suggested the active excretion is probably an important pathway for the insect to eliminate myclobutanil rapidly with nonenantioselectivity as a passive transport process, which was consistent with the low accumulation efficiency of myclobutanil measured by BAF (bioaccumulation factor). Chirality 25:890–896, 2013. © 2013 Wiley Periodicals, Inc.  相似文献   

3.
Myclobutanil, (RS)‐2‐(4‐chlorophenyl)‐2‐(1H‐1, 2, 4‐triazol‐1‐ylmethyl)hexanenitrile is a broad‐spectrum systemic triazole fungicide which consists of a pair of enantiomers. The stereoselective degradation of myclobutanil was investigated in rat liver microsomes. The concentrations of myclobutanil enantiomers were determined by high‐performance liquid chromatography (HPLC) with a cellulose‐tris‐(3,5‐dimethyl‐phenylcarbamate)‐based chiral stationary phase (CDMPC‐CSP) under reversed phase condition. The t1/2 of (+)‐myclobutanil is 8.49 min, while the t1/2 of (–)‐myclobutanil is 96.27 min. Such consequences clearly indicated that the degradation of myclobutanil in rat liver microsomes was stereoselective and the degradation rate of (+)‐myclobutanil was much faster than (–)‐myclobutanil. In addition, significant differences between two enantiomers were also observed in enzyme kinetic parameters. The Vmax of (+)‐myclobutanil was about 4‐fold of (–)‐myclobutanil and the CLint of (+)‐myclobutanil was three times as much as (–)‐myclobutanil after incubation in rat liver microsomes. Corresponding consequences may shed light on the environmental and ecological risk assessment for myclobutanil and may improve human health. Chirality 26:51–55, 2013. © 2013 Wiley Periodicals, Inc.  相似文献   

4.
Liu HJ  Cai WD  Huang RN  Xia HL  Wen YZ 《Chirality》2012,24(2):181-187
Cyclodextrins (CDs) possess a variety of chiral centers and are capable of recognizing enantiomeric molecules through the formation of inclusion complexes. Two types of CDs, α-cyclodextrin (α-CD) and β-cyclodextrin (β-CD), were selected to evaluate the effects of the enantioselective ecotoxicity of racemic metolachlor (Rac-metolachlor) and its S-enantiomer (S-metolachlor) on the freshwater algae Scenedesmus obliquus (S. obliquus) by acute toxicity test. The results showed that the aquatic toxicity of S-metolachlor was higher than Rac-metolachlor and that CDs enhanced the toxicity of metolachlor enantioselectively by increasing the aquatic toxicity of Rac-metolachlor rather than that of S-metolachlor to S. obliquus. The equilibrium constant for Rac-metolachlor-CD complexes was higher than that of S-metolachlor-CDs, which was responsible for the greater aquatic toxicity shift effect of Rac-metolachlor. Thermodynamic studies of CD complexes showed that inclusion for all of the complexes was primarily a spontaneous, enthalpy-driven process. These results will help to understand the preliminary mechanism of shifting aquatic toxicity of metolachlor by CDs and the CDs mediated environmental processes of metolachlor, to correctly apply CDs to chiral pesticides formulation and environmental remediation of chiral contaminants.  相似文献   

5.
Lu D  Huang L  Diao J  Zhou Z 《Chirality》2012,24(6):481-485
Chiral compounds usually behave enantioselectively in phyto‐biochemical processes. Isocarbophos (ICP) is a chiral pesticide that is widely used. To evaluate the toxicological response of ICP and its enantiomers to Scenedesmus obliquus, algal growth, total chlorophyll, total soluble protein, and the superoxide anion radicals (O2?‐) were investigated. The microalgae were treated with ICP and its enantiomers at 0.01–10 mg/l for 96 h. The growth of S. obliquus was stimulated at low levels of ICP and its enantiomers (0.01–1 mg/l), but all were inhibited at high concentrations (10 mg/l). The total soluble protein content and total chlorophyll content of the tested green alga S. obliquus gradually increased, depending on the growth of algal cells in the medium. Meanwhile, the content of O2?‐ was decreased. Interestingly, the cell number and content of the chlorophylls and protein decreased with increasing levels of concentration, whereas O2?‐ increased. Our results indicated that enantioselectivity was observed in the dose–response of ICP and its enantiomers in S. obliquus. The high O2?‐ level might lead to the death of S. obliquus. The stimulation of growth suggests a regulatory mechanism that is related to the capability of the algae to adapt to the O2?‐. Chirality 24:481–485, 2012. © 2012 Wiley Periodicals, Inc.  相似文献   

6.
斜生栅藻中虾青素的积累过程及其光合活性变化   总被引:1,自引:1,他引:0  
分析了斜生栅藻(Scenedesmus obliquus)在光温(30℃,180 μmol/m2·s)胁迫条件下积累虾青素的过程,观察了该过程中细胞形态及细胞光合生理的变化。胁迫条件下,细胞在48h内生成并积累了包括海胆酮、角黄素、金盏花黄素和金盏花红素在内的多种次生类胡萝卜素,并合成了虾青素及其酯。该过程中,细胞形态由两端尖细变得不规则、膨大,原来由4、8个细胞组成的定形群体变为游离的单个细胞或2个细胞组成的群体。藻细胞光合速率在24h内先下降后上升,而后又呈现下降趋势,从34.29 μmol O2/mg Chla/h迅速下降为5.21 μmol O2/mg Chla/h;呼吸速率在前24h内升高至60.37 μmol O2/mg Chla/h,而后缓慢下降到38.40 μmol O2/mg Chla/h;光合系统Ⅱ的活性随着胁迫时间的延续而逐步下降,较初始值降低了63.9%。结果表明,斜生栅藻细胞在高光照条件下可以合成虾青素,并通过调节光合速率、呼吸速率以及光合系统Ⅱ的效率来应对胁迫。  相似文献   

7.
Photosynthetic capacity and quantum requirement of photosynthesis were evaluated in three secondary mutants of Scenedesmus obliquus possessing specific blocks in carotenoid biosynthesis. These were derived from the mutant, C-2 A', a strain which develops chlorophyll only in the light. All strains were capable of a normal and rapid production of chlorophyll and the development of a functional photosynthetic apparatus when exposed to light. LHC-II levels in the mutants lacking the β,ε-carotenoids (strains C-2 A'-34,1 and C-2 A'-67, 3b) were considerably reduced in fully greened cells but normal in the β,β-epoxycarotenoid deficient-only strain (C-2 A'-67,1) (Bishop, 1996). The maximum photosynthetic capacity and the quantum efficiency (at λ=682nm) of photosynthesis of cells of C-2A'-34,1 and C-2 A'-67,1 showed no significant changes when compared to the original parent strain, C-2 A'. However, the quantum requirement of the strain lacking both types of carotenoids, C-2 A'-67,3b, was slightly increased. It is of particular interest that both strains lacking the β,ε-carotenoids also show a preferential loss of the oligomeric form of the LHC and its associated chlorophylls. The potential requirement of the different carotenoids in maintenance of photosynthetic efficiency in Scenedesmus is discussed.  相似文献   

8.
Myclobutanil, (RS)‐2‐(4‐chlorophenyl)‐2‐(1H‐1, 2, 4‐triazol‐1‐ylmethyl) hexanenitrile is a widely used triazole fungicide. In this study, enantioselective metabolism and cytotoxicity were investigated in rat hepatocytes by chiral HPLC‐MS/MS and the methyl tetrazolium (MTT) assay, respectively. Furthermore, tryptophan metabolism disturbance in rat hepatocytes after myclobutanil exposure was also evaluated by target metabolomics method. The half‐life (t1/2) of (+)‐myclobutanil was 10.66 h, whereas that for (?)‐myclobutanil was 15.07 h. Such results indicated that the metabolic process of myclobutanil in rat hepatocytes was enantioselective with an enrichment of (?)‐myclobutanil. For the cytotoxicity research, the calculated EC50 (12h) values for rac‐myclobutanil, (+)‐ and (?)‐myclobutanil were 123.65, 150.65 and 152.60 µM, respectively. The results of tryptophan metabolites profiling showed that the levels of kynurenine (KYN) and XA were both up‐regulated compared to the control, suggesting the activation effect of the KYN pathway by myclobutanil and its enantiomers which may provide an important insight into its toxicity mechanism. The data presented here could be useful for the environmental hazard assessment of myclobutanil. Chirality 27:643–649, 2015. © 2015 Wiley Periodicals, Inc.  相似文献   

9.
It is demonstrated that chlorophyll b does not only derive from chlorophyll a , but is also formed separately from an in vivo-occurring chlorophyllide b . The branching point for the latter synthesis is at the level of chlorophyllide, since no protochlorophyllide b was detectable. We have indications that the enzyme oxidizing chlorophyll a to chlorophyll b accepts also non-phytylated 17,18 dihydroporphyrins and is not restricted to chlorophylls. Preparations of chlorophyllide a and chlorophyll a could both be transferred with the same enzyme fraction to chlorophyllide b and chlorophyll b , respectively. Preliminary experiments show this enzyme to be membrane bound and light independent. An updated scheme for chlorophyll b biosynthesis is presented.  相似文献   

10.
The effect of acetate on growth and rate of ammonium uptake in Scenedesmus obliquus (UTEX 78) was investigated under light-limiting conditions. Addition of acetate to autotrophic cells with a growth constant of 0.71 day−1 resulted in an increase in the growth rate (mixotrophy, k = 1.3 day−1), and in the presence of acetate, growth occurred in the dark (heterophy, k = 0.44 day−1). The rate of ammonium uptake in autotrophy (17.8 amol cell−1 min−1) was similar to that in heterotrophy (17.4 amol cell−1 min−1) but was 3.7 times lower than that in mixotrophy (65.9 amol cell−1 min−1). In general, mixotrophic cells showed optimum ammonium uptake at the acetate concentration at which they were grown. In autotrophy, uptake of ammonium leveled off at about 12.5 μ M while no saturation was observed in mixotrophic cells. An increase in the rate of uptake of ammonium was observed in autotrophic cells within 1 h after the addition of acetate. The activity of isocitrate lyase (EC 4.1.3.1), a key enzyme for the regulation of the glyoxylate cycle responsible for acetate catabolism, showed a 3.9-fold increase in activity after 24 h in the dark in the presence of acetate. The level of isocitrate lyase activity in cells grown for 24 h in the dark in the presence of 0–20 m M acetate also increased as a function of acetate concentration.  相似文献   

11.
The pigment mutant C-2A' of the unicellular green alga Scenedesmus obliquus accumulates protochlorophyllide and small amounts of protochlorophyll in darkness. Protochlororphyll was isolated and characterized by thin layer chromatography and absorption and fluorescence spectroscopy. The protochlorophyll was photoreduced by light to chlorophyll both in vitro and in vivo.  相似文献   

12.
Abstract

A Potentiometric titration method was used to study the adverse effect of arsenate (As(V)) and arsenite (As(III)) on inorganic carbon uptake in suspensions of the green alga Scenedesmus obliquus. The measurements were performed in a closed CO2-system with diluted synthetic seawater (1‰ salinity) as ionic medium. Usually, the algal chlorophyll concentration was 0.4 mg dm?3, while the arsenate- and arsenite-concentrations were varied within the limits 0.1 to 200 μmol dm?3. In some experiments arsenate toxicity was studied in the presence of 1 to 100 μmol dm?3 of phosphate (P(V)).

With concentrations of arsenate or arsenite less than 0.1 μmol dm?3 no toxic effects were observed. However, at As-concentrations of 200 μmol dm?3, the algal carbon uptake was reduced by 41% with arsenate and 29% with arsenite, i.e., arsenate is more toxic to Scenedesmus obliquus than arsenite. The toxicity of arsenate was negligible in the presence of a ten fold excess of phosphate. This is probably due to chemical similarities between arsenate and phosphate causing competition between the ions for the binding sites.

The importance of taking the speciation as well as the buffer capacity of the algal system into account, when calculating the carbon uptake, is also discussed.  相似文献   

13.
The behavior and mechanisms of the enantioselective degradation of beta‐cypermethrin were studied in soil. The four isomers were degraded at different rates, and the enantiomer fractions of alpha‐cypermethrin and theta‐cypermethrin exceeded 0.5. Moreover, 3‐phenoxybenzoic acid, phenol, and protocatechuic acid were detected; based on the presence of these metabolites, we predicted the degradation pathway and identified the functional genes that are related to this degradation process. We established quantitative relationships between the data on degradation kinetics and functional genes; we found that the quantitative relationships between different enantiomers differed even under the same conditions, and the genes pobA and pytH played key roles in limiting the degradation rate. Data obtained using path analysis revealed that the same gene had different direct and indirect effects on the degradation of different isomers. A mechanism was successfully proposed to explain the selective degradation of chiral compounds based on the perspective of functional genes. Chirality 27:929–935, 2015. © 2015 Wiley Periodicals, Inc.  相似文献   

14.
杨州  孔繁翔  史小丽  张民 《生态学报》2008,28(4):1857-1863
分离自太湖的壶状臂尾轮虫(Brachionus urceus (Linnaeus))按1000 ind·L-1的密度置于斜生栅藻(Scenedesmus obliquus)中培养24h后,用孔径0.10 靘的微孔滤膜抽滤,得到壶状臂尾轮虫培养滤液.将壶状臂尾轮虫培养滤液以20%的比例添加到纯培养的斜生栅藻中,进行为期7d的试验.结果表明壶状臂尾轮虫培养滤液能显著地影响斜生栅藻的形态,处理组中诱发性多细胞群体增加,导致处理组中斜生栅藻种群平均每个个体的细胞数量显著高于对照组.斜生栅藻在壶状臂尾轮虫诱发下形成群聚体可以解释为一种诱发性的反牧食防御,同时也进一步证实了栅藻对浮游动物牧食的响应是一种广泛存在的现象.壶状臂尾轮虫培养滤液处理后的斜生栅藻在生长率上与对照组没有显著性差异,说明诱发性防御群聚体形成的代价没有体现在对生长的影响上.在壶状臂尾轮虫培养滤液诱发下,较多栅藻细胞聚积在一起形成群聚体后,栅藻溶解性胞外多聚糖和固着性胞外多聚糖均有显著提高,而胞内多聚糖略有下降.但从总多聚糖含量看,处理组明显高于对照组,这也说明轮虫培养滤液刺激了栅藻多聚糖合成的额外增加,且被分泌到胞外,充当细胞之间的粘合物,促使细胞容易聚合形成群聚体,有效防御象轮虫这些小型浮游动物的进一步牧食,保持种群得以延续.  相似文献   

15.
渍水对油菜苗期生长及生理特性的影响   总被引:3,自引:0,他引:3  
通过盆栽试验研究了模拟渍水条件对苗期油菜(Brassica napus L.)中双11号生长及生理特性的影响。结果表明,渍水超过3 d就会显著抑制苗期油菜的生长,这与渍水降低油菜叶片叶绿体和光合色素含量、降低氮素吸收利用和引起过氧化胁迫有关。渍水后苗期油菜的生理恢复,无论是叶绿体和光合色素含量,还是硝酸还原酶及抗氧化酶活性的恢复均表现出一定的滞后性,而且渍水时间越长滞后期越长。此外,在苗期油菜叶片光合色素中,渍水对类胡萝卜素的影响要大于对叶绿素的影响。  相似文献   

16.
苯并(a)芘对大弹涂鱼肝脏过氧化氢酶活性的影响   总被引:9,自引:0,他引:9  
过氧化氢酶 (CAT)是生物体内一种含巯基 ( -SH)的抗氧化酶 ,可与谷胱甘肽过氧化物酶一起 ,清除超氧化物歧化酶歧化超氧阴离子自由基(O2 - )产生的过氧化氢 (H2 O2 ) ,进而阻断可产生活性极高的羟自由基 (OH)的Haber Weiss反应 :M O2 - H2 O2 →M2 OH OH O2 (M 为金属离子 ) ,因而在生物体的抗氧化防御系统中占有重要地位[1 2 ] 。研究表明 ,包括CAT在内的抗氧化防御系统的成分可由于氧化污染的胁迫而发生改变 ,尝试以这些抗氧化防御系统成分的变化作为氧化胁迫的生物指标的研究正在成为毒理学研究的…  相似文献   

17.
为探索浮游动物和藻类之间可能存在的信息传递,研究了萼花臂尾轮虫培养滤液对铜绿微囊藻、斜生栅藻和小球藻的生长及群体形成的影响.把萼花臂尾轮虫按1000个·L-1的初始密度置于小球藻中培养24h后,用孔径0.15μm的微孔滤膜抽滤,得到轮虫培养滤液,此滤液中含有轮虫在生活过程中释放的一些信息化学物质.将轮虫培养滤液以20%的比例分别加入纯培养的铜绿微囊藻、斜生栅藻和小球藻中,进行为期7d的试验.结果表明,萼花臂尾轮虫培养滤液能显著地促进斜生栅藻的群体形成,而对铜绿微囊藻和小球藻在群体形成方面没有显著作用.另外,该滤液能显著提高小球藻种群的增长,对铜绿微囊藻和斜生栅藻的生长无明显影响.3种藻类对萼花臂尾轮虫的潜在牧食采取了不同的生态策略:斜生栅藻形成群体,增大摄食阻力,从而降低被摄食的风险;小球藻通过提高增长率来抵消被取食的损失;铜绿微囊藻是通过其它方式来降低被牧食(例如毒素).这些方式分别是这些藻类维持种群规模的反牧食防御策略之一.  相似文献   

18.
研究了浓度为0、1、5、10、15、20 mg/L的新兴离子液体溴化1-己基-3-甲基咪唑([C6mim]Br)在24h、48h、72h和96h对斜生栅藻还原型谷胱甘肽(GSH)及其代谢酶-谷胱甘肽过氧化物酶(GPX)、谷胱甘肽转硫酶(GST)和谷胱甘肽还原酶(GR)的影响。结果表明:GSH含量在24h、48h和72h时,在最低处理浓度下不变,其他处理浓度下随胁迫浓度增加而降低,96h时则与对照无差异或较小;GPX和GST的活性在72h之前明显升高(最高浓度组的GST活性有波动),96h时均降低至对照水平;GR活性在24h时,[C6mim]Br=1 mg/L时升高,之后降低,在48h增高至对照水平,72h时,[C6mim]Br≥10 mg/L的处理组高于对照水平,96h时,除最低处理组外,均降至对照水平以下。GR是GSH系统中的限速酶,GST则是该系统中活性和灵敏性最高的酶,可作为[C6mim]Br胁迫时的敏感的生物标志物。1 mg/L的[C6mim]Br可引起藻细胞的氧化胁迫,具有环境毒性。  相似文献   

19.
W. G. Hei  H. Senger 《Planta》1986,167(2):233-239
The phosphorylation of thylakoid proteins, which comprise apoproteins of the light-harvesting chlorophyll a/b-protein complex (LHCP), was investigated in vivo and in vitro during the development of Scenedesmus obliquus in synchronous cultures. The in-vitro and in-vivo protein phosphorylation exhibited a maximum activity in cells with maximum photosynthetic capacity (8th hour) and miximum activity in cells with minimum photosynthetic capacity (16th hour). The major phosphorylated polypeptides in vivo were the 24/25-kDa and 28–30-kDa apoprotein of the LHCP, a protein of about 32 kDa, and some smaller polypeptides within the range 10 to 20 kDa. In vitro, the main phosphoproteins were the 28–30-kDa apoprotein and the protein characterized by an apparent molecular weight of 32 kDa. Pulse-chase experiments in vivo established that the latter had the fastest radioactivity turnover of the thylakoidal phosphoproteins.Abbreviations DCMU 3-(3,4-dichlorophenyl)-1,1-dimethylurea - LHCP light-harvesting chlorophyll a/b-protein complex - PSII photosystem II Dedicated to Prof. Erwin Bünning on the occasion of his 80th birthday  相似文献   

20.
The wild type (WT) of Scenedesmus obliquus and a mutant lacking chlorophyll b and the light-harvesting complexes (WT-LHC1) were synchronized by a light-dark regime. Both cultures contained the same type of carotenoids. However, concentrations and patterns of carotenoids were different during their synchronous life cycles. The concentration of total carotenoids followed more or less that of chlorophyll. The WT contained more carotenoids per cell mass, but slightly less per chlorophyll. It is discussed that part of the carotenoids of the mutant, lacking the peripheral antenna of PSII, might be located in the chlorophyll b-less apoprotein or in an enlarged core antenna of PSII. During the life cycle of Scenedesmus the carotenes are initially synthesized and most of the α-carotene is immediately oxidized to lutein which is inserted in the antennae systems of PSII and PSI. The further oxidation of lutein to loroxanthin seems to depend on both the change from dark to light, and on stages of the life cycle itself. Although the major part of β-carotene appears to be inserted in the reaction centers, a fraction of the total pool is rapidly converted to violaxanthin, following the onset of illumination. The conversion may serve to protect against photooxidation. Further conversion of violaxanthin to neoxanthin occurs to a greater extent in the mutant, WT-LHC1. The results demonstrate (1) the close connection between the carotenoid pattern and the modulation of the photosynthetic apparatus during the life cycle of Scenedesmus and (2) the flexibility of the organism in compensating for the absence of the light-harvesting complexes of photosystems II by adjusting the carotenoid distribution.  相似文献   

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