[4 + 6]-cycloaddition von 1,3-butadien an hexacarbonyl-μ-η6:6-heptafulvalen-dichrom(0)

The thermal reaction of heptafulvalene (I) with [Cr(CO)₃(CH₃CH)₃] (II) gives the hexacarbonyl-η^6:6-heptafulvalenedichromium(0) complex (III). UV irradiation of complex III in THF solution, with 1,3-butadiene (IV) in successive [4 + 6]-cycloadditions and decomplexations gives the complexes tricarbonyl-η⁶-11-(2,4,6-cycloheptatrien-1-ylidene)bicyclo[4.4.1]undeca-2,4,8-trine-chromium(0) (V) and tricarbonyl-η⁶-bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene)-chromium(0) (VI). On warming, VI looses the bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene) hydrocarbon ligand (VII). The reaction of VII with [Mo(CO)₃(diglyme)] (VIII) gives the tricarbonyl-η⁶-bi(bicyclo[4.4.1]undeca-2,4,8-trien-11-ylidene)molybdenum(0) complex (IX). The compounds III, V–VII and IX were characterized by IR and NMR spectra (¹H, ¹³C) and by C,H elemental analysis.     

Dissipation,residue, and distribution of pyraclostrobin in banana and soil under field conditions in South China

Two independent field trials were conducted in Guangdong and Guangxi, South China, in 2013, to study the dissipation, residue levels, and distribution of pyraclostrobin in banana and soil under field conditions. Pyraclostrobin residues were determined through a quick and effective method of high-performance liquid chromatography. Results showed that the average recoveries ranged from 80.55% to 98.08%, with relative standard deviations of 3.18–7.81% at three different spiking levels for each different matrix. The quantification limit of the proposed method was 0.006 mg/kg for both banana and soil. The half-lives of pyraclostrobin in bananas were 9.09 days in Guangdong and 8.26 days in Guangxi, and both bananas exhibited a dissipation rate of 90% after 28 days. The half-lives of pyraclostrobin in soil were 11.61 days in Guangdong and 10.60 days in Guangxi, with a dissipation rate of 90% after 35 days. Although several positive banana samples (i.e., pyraclostrobin exceeding the maximum residue limits (MRL) were found, the terminal residues in banana pulp were not detectable. All the terminal residues in banana pulp were below the MRL of 0.02 mg/kg, set by the Chinese Ministry of Agriculture, indicating a negligible risk associated with the exposure to pyraclostrobin via the consumption of banana. The distribution of pyraclostrobin in soil was also investigated in two experimental sites. The pyraclostrobin in different layer soil was time dependent and did not vary between the two sites. The result also showed that pyraclostrobin could be easily transported from the top soil to the subsoil. However, the highest quantity ratio did not exceed 10% in the bottom layer (20–30 cm). The distribution assessment also revealed that no significant potential environment risk was induced by pyraclostrobin in bananas.     

新型手性杀虫剂唑虫酯异构体拆分及其在蔬菜中的分析方法建立

以全新手性杀虫剂唑虫酯为研究对象,通过筛选手性色谱柱和优化流动相比例,建立了唑虫酯及其氧化代谢物异构体的拆分方法,在此基础上开发利用高效液相色谱-串联质谱(HPLC-MS/MS)同时测定小白菜和蕹菜中唑虫酯及其氧化产物手性异构体的分析方法。以纤维素-三(3,5-二氯苯基氨基甲酸酯)共价键合手性柱(Chiral INC)(250 mm×4.6 mm, 5 μm)为分析柱,乙腈和2 mmol/L甲酸铵水溶液作为流动相进行梯度洗脱分离,在多反应监测负离子模式下进行检测,唑虫酯4个异构体分离度分别为1.63、2.83和1.74,唑虫酯氧化产物异构体分离度为5.82。通过衍生化的方法进一步确定出峰顺序为RS-唑虫酯、SS-唑虫酯、RR-唑虫酯、SR-唑虫酯、S-唑虫酯氧化产物和R-唑虫酯氧化产物。唑虫酯和其氧化产物的手性异构体分别在1.25~1250 μg/L和2.5~2500 μg/L范围内具有良好的线性关系,相关系数(R²)大于0.99。在蕹菜和小白菜样品中同时添加唑虫酯和唑虫酯氧化产物消旋体进行添加回收试验,添加水平为1、20、400 μg/kg(即唑虫酯异构体为0.25、5、100 μg/kg;唑虫酯氧化代谢产物异构体为0.5、10、200 μg/kg),回收率为72.6%~110.6%,相对标准偏差(RSD)均在9.4%以下,其中日内重复性的RSD在0.5%~9.4%之间;日间重复性的RSD在1.0%~8.6%之间,表明该方法具有良好的回收率和精密度。该研究可为唑虫酯这一新型手性农药的环境行为研究及后续质量控制、药效评价等提供相应的分析技术,为新农药开发应用提供有力的技术支撑。     

The removal of Cu,Ni, and Zn in industrial soil by washing with EDTA-organic acids

In order to improve the heavy metal removal ability of traditional single washing agents and explore the removal mechanism of heavy metals. Then, the washing reagents that mixed by low-molecular weight organic acids (citric acid, oxalic acid, and tartaric acid) and artificial chelating compound ethylenediaminetetraacetic acid disodium (EDTA) were selected. Furthermore, the effect of soil washing parameters, the variation of leaching toxicity, mobility, stability and speciation of heavy metals were also considered. The results of soil washing experiments showed that mixing an equal volume of 0.05 M EDTA and 0.2 M organic acids (citric acid, oxalic acid, and tartaric acid) could remove more than about 80% heavy metals from soil under the optimal conditions. In addition, the soil leaching toxicity was decreased and the stability of remaining heavy metals was increased, indicating that EDTA-organic acid washing reagents could effectively reduce the ecological risk of contaminated soil. EDTA had a stronger chelating ability with heavy metals than the organic acids, and the organic acids could not only chelate heavy metals but also decrease the pH of the mixture for promoting the desorption of heavy metals. Thus, mixing EDTA and organic acids was advisable method to improve soil washing technology.     

基于Mask R-CNN网络的磨损颗粒智能识别与应用

针对设备磨损故障诊断中磨粒识别技术难度高、工作主观经验影响大等问题,采用深度学习技术开展了磨粒智能识别的研究,提出了基于Mask R-CNN卷积神经网络的磨粒数字化表征方法. 该方法利用迁移学习训练基于Mask R-CNN网络的磨粒识别模型对图像中磨粒进行识别和实例分割,然后使用Suzuki85算法、迭代算法、等比例计算方法计算出磨粒的真实尺寸,解决了磨粒分析中难定量分析的问题. 结果表明:基于Mask R-CNN网络(采用R-101-FPN骨干网络)训练的磨粒识别模型可以对图像中多个异常磨损颗粒进行识别,综合准确率和召回率达到当前图像识别领域的主流水平. 辅以上述Suzuki85等算法,成功实现磨粒图像的定量评价分析,对促进设备故障诊断技术的自动化发展和工业应用具有一定的实际应用价值.      

Synthesis,DNA-binding,molecular docking and cytotoxic activity in vitro evaluation of ruthenium(II) complexes

Transition Metal Chemistry - Five new ruthenium(II) polypyridyl complexes [Ru(N–N)2(BTCP)](ClO4)2 (BTCP?=?2-(bicyclo[2.2.1]hept-5-en-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline;...     

Periodic solutions of nonlinear functional difference equations at nonresonance case

Sufficient conditions for the existence of at least one T-periodic solution of nonlinear functional difference equation

Δx(n)+a(n)x(n)=f(n,u(n)),     

Unconventional trapping of ultracold neutrons

In unconventional storage experiments we filled ultracold neutrons (UCN) into a Fomblin-grease coated trap and then immediately removed the UCN from the storage volume by an absorber, until their residual density in the trap was measured to be negligible. When subsequently the absorber was withdrawn a significant number of UCN of higher energies emerged from the trap. Their appearance cannot be attributed to heating or cooling of residual UCN. Further experiments were performed to investigate the origin of these UCN which we call `late UCN'. We noticed that application of a magnetic field gradient at the trap wall as well as a replacement of Fomblin grease on the surface by Fomblin oil gave rise to small but measurable alterations of storage behavior. These phenomena are consistent with the hypothesis of temporary adhesion of a few UCN to a rough wall.     

Thermodynamics of spinning D3-branes

Spinning black 3-branes in type IIB supergravity are thermodynamically stable up to a critical value of the angular momentum density. Inside the region of thermodynamic stability, the free energy from supergravity is roughly reproduced by a naive model based on free N = 4 super-Yang-Mills theory on the world-volume. The field theory model correctly predicts a limit on angular momentum density, but near this limit it does not reproduce the critical exponents one can compute from supergravity. Analogies with Bose condensation and modified matrix models are discussed, and a mean field theory improvement of the naive model is suggested which corrects the critical exponents.