Generation and analysis of mixed chlorinated/brominated homologs of the halogenated natural product heptachloro-1'-methyl-1,2'-bipyrrole

The 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1, MBP-79) and further halogenated 1′-methyl-1,2′-bipyrroles (MBPs) are a class of marine natural products repeatedly detected in seafood and marine mammals from all over the world. Only Q1 is currently commercially available as reference standard and the full synthesis of mixed brominated-chlorinated compound is rather complicated. For this reason, synthetic Q1 (240 mg) was transferred into bromine-containing MBPs by UV-irradiation in the presence of bromine. Bromine, which rapidly vanished from the solutions, was re-newed during the reaction in order to generate higher amounts of Br-containing MBPs. A total of ∼150 mg Q1 was transferred after ∼10 min irradiation with high amounts of Br₂ to give 30.5 mg BrCl₆-MBPs along with lower proportions of Br₂Cl₅-, Br₃Cl₄-, Br₄Cl₃- and traces of Br₅Cl₂-MBPs. Longer UV-irradiation in the presence of Br₂ even allowed for the detection of Br₆Cl-MBPs and traces of Br₇-MBP. However, this reaction also provided some unknown by-products. A sample stored in the dark and later in in-door light (no UV irradiation) also eliminated Q1 after 76 d in favour of heptahalogenated MBPs with up to three bromine substituents. The irradiation products were separated on silica, and fractions containing only Q1 and BrCl₆-MBPs were then further fractionated by non-aqueous RP-HPLC. A pure isolate of the major BrCl₆-MBP (∼1.5 mg) was characterized by GC/MS and ¹³C NMR to be 2-bromo-3,3′,4,4′,5,5′-hexachloro-1-methyl-1,2′-bipyrrole (Br-MBP-75). Partial GC enantioseparation of the axially chiral Br-MBP-75 was achieved on a β-PMCD column. A full enantioseparation was managed by enantioselective HPLC using a NUCLEOCEL DELTA S column. Low amounts of pure BrCl₆-MBP enantiomers could be trapped.     

微波炉快速测定城市污泥湿度的探讨

用额定电压为220 V、振荡频率为2 450 MHz、输出功率为800 W的微波炉对5～30 g城市污泥辐照2～30 min。由不同时间对城市污泥进行微波辐照后的质量损失率、残余湿度以及挥发性固体（VS）含量的变化表明：用微波炉可简便、快速地测定城市污泥的湿度。为提高微波炉测定湿度的准确性,应减少取样量,进行重复辐照,并根据相邻2次辐照导致的质量变化幅度逐次缩短辐照时间;在辐照过程中应避免引起样品突然释放大量VS,辐照至恒重为止。     

Using LiDAR Data Analysis to Estimate Changes in Insolation Under Large‐Scale Riparian Deforestation1

Greenberg, Jonathan Asher, Erin L. Hestir, David Riano, George J. Scheer, and Susan L. Ustin, 2012. Using LiDAR Data Analysis to Estimate Changes in Insolation Under Large‐Scale Riparian Deforestation. Journal of the American Water Resources Association (JAWRA) 48(5): 939‐948. DOI: 10.1111/j.1752‐1688.2012.00664.x Abstract: Riparian vegetation provides shade from insolation to stream channels. A consequence of removing vegetation may be an increase in insolation that can increase water temperatures and negatively impact ecosystem health. Although the mechanisms of riparian shading are well understood, spatially explicit, mechanistic models of shading have been limited by the data requirements of precisely describing the three‐dimensional structure of a riparian corridor. Remotely acquired, high spatial resolution LiDAR data provide detailed three‐dimensional vegetation structure and terrain topography over large regions. By parameterizing solar radiation models that incorporate terrain shadowing with LiDAR data, we can produce spatially explicit estimates of insolation. As a case study, we modeled the relative change in insolation on channels in the Sacramento‐San Joaquin River Delta under current conditions and under a hypothesized deforested Delta using classified LiDAR, rasterized at a 1‐m resolution. Our results suggest that the removal of levee vegetation could result in a 9% increase in solar radiation incident on Delta waters, and may lead to water temperature increases. General, coarse‐scale channel characteristics (reach width, azimuth, levee vegetation cover, and height) only accounted for 72% of the variation in the insolation. This indicates that the detailed information derived from LiDAR data has greater explanatory power than coarser reach‐scale metrics often used for insolation estimates.     

Effect of humic acids on photodegradation of chloroacetanilide herbicides under UV irradiation

The effects of two humic acids (HAs) of different origins on the photodegradation of the chloroacetanilide herbicides acetochlor, propisochlor and butachlor were investigated in this study. One of the tested HAs was a standard sample that was purchased from a commercial source, and the other was isolated from the black soil of Northeast China. The photolysis of all three herbicides followed pseudo-first-order kinetics under ultraviolet (UV) irradiation conditions, regardless of whether HAs were present or not. Both HAs improved the photolysis rates of acetochlor in a dose-reversed way, whereas they inhibited butachlor degradation under all experimental concentrations. The two HAs differed in their effects on propisochlor photolysis, changing from enhancement to inhibition, depending on the origin and concentration of HAs. Element and Fourier Transform Infrared spectroscopy analyses showed that the isolated HAs had more polysaccharides and less aliphatic groups than the commercial HAs, and it was indicated that some characteristic radicals (C═O, O─H and phenolic hydroxyls) in HAs were involved in the photolysis of the herbicides. Gas chromatography/mass spectrometry (GC/MS) analyses indicated that the presence of HAs had no effects on the photolysis pathway and photoproduct species of the three herbicides.     

Microwave synthesis and antifungal evaluations of some chalcones and their derived diaryl-cyclohexenones

Microwave irradiation (MWI) of acetophenones and substituted benzaldehydes in water resulted in a “green-chemistry” procedure for the preparation of chalcones (1-14), through base catalyzed Claisen-Schmidt condensation reaction, in good yields. Further 3,5-diaryl-6-carbethoxy-2-cyclohexen-1-ones (1a-14a) were prepared through base catalyzed cyclocondensation of above chalcones with ethylacetoacetate using MWI as the energy source and silica as support. Out of fourteen cyclohexenones, ten (1a, 4a, 5a, 6a, 7a, 9a, 10a, 11a, 12a and 13a) are reported for the first time in literature. The synthesized compounds were characterized using various spectroscopic techniques, viz. (¹H NMR and IR) and screened for their antifungal activity in vitro against Sclerotium rolfsii and Rhizoctonia solani by poisoned food technique. The compounds tested were found to be active against R. solani whereas against S. rolfsii, moderate activity was observed, as evident from LC₅₀ values. The most potent compounds against R. solani were 1-(4-Fluoro-phenyl)-3-phenyl-propenone (13) and 1,3-Diphenyl-propenone (14) having LC₅₀ values of 2.36 and 2.49 mgL^{? 1} respectively (LC₅₀ of Hexaconazole = 1.12 mgL^{? 1}) and against S. rolfsii 3-(4-Fluoro-phenyl)-5-(3-nitro-phenyl)-6-carbethoxy-2-cyclohexen-1-one (12a) was most active having LC₅₀ value of 285 mgL^{? 1}compared to Hexaconazole (LC₅₀ = 1.27 mgL^{? 1}).     

磁性竹基炭对Pb2+、Cd2+与Cu2+的吸附机理研究

采用微波辐照技术,以枯竹子为碳源制备了磁性竹基炭(BBMC),并将其用于对重金属离子Pb2+、Cd2+与Cu2+的吸附去除.同时,分析了吸附时间、pH值、离子强度及初始金属离子浓度等条件对吸附的影响,讨论了BBMC对3种金属离子的吸附特性与吸附机理.结果表明,金属离子在BBMC上的吸附符合Langmuir等温模式和准二级动力学吸附方程;吸附的机理可归结为金属阳离子与BBMC上的H+之间的离子交换作用,且吸附能力可能与金属离子半径有关,呈现出Pb2+Cd2+Cu2+的趋势,重金属离子Pb2+、Cd2+与Cu2+的最大平衡吸附量分别为16.2、14.0和9.5 mg·g-1.     

反应堆压力容器材料中Ni界面偏析对富Cu溶质团簇演化影响的模拟研究

目的定量研究镍原子的界面偏析对降低团簇与基体间表面能及促进团簇形核、提升团簇数密度的贡献,以深化对反应堆压力容器溶质团簇演化过程和辐照脆化中溶质团簇机理的认识。方法通过考虑Fe-Cu-Ni三元合金溶质团簇中镍原子的界面偏析,利用团簇动力学方法研究了团簇中镍原子分布对富铜溶质团簇演化的影响。结果相比铜团簇,加入镍原子后的铜镍团簇自由能显著降低,团簇数密度显著提高;随团簇中镍原子界面偏析加剧,团簇自由能与团簇尺寸逐渐下降,团簇数密度先小幅上升,后下降。结论镍可以促进富铜溶质团簇的形核,提升团簇的数密度,而其中镍原子的界面偏析对促进团簇形核的贡献可能有限;在团簇生长过程中,镍原子的界面偏析可能会抑制其生长,减小团簇的尺寸。     

双氯芬酸钠水溶液的辐照降解

利用60Coγ射线辐照双氯芬酸钠水溶液,探讨了不同辐照剂量下初始浓度、自由基促进剂和淬灭剂、水体共存物质等因素对降解的影响,研究其降解途径,并和等离子体放电降解效果进行了对比.结果表明,γ辐照可有效降解双氯芬酸钠,但矿化过程要长于降解过程,当初始浓度为20.5、30.4和50.1 mg·L-1时,反应动力学常数分别为2...     

Microwave and Fenton's reagent oxidation of wastewater

We compared two H₂O₂ oxidation methods for the treatment of industrial wastewater: oxidation using Fenton's reagent [H₂O₂/Fe(II)] and microwave irradiation. Both methods were applied to the treatment of synthetic phenol solutions (100 mg L⁻¹) and of an industrial effluent containing a mixture of ionic and non-ionic surfactants at high load (20 g L⁻¹ of COD). The effects of initial pH, initial H₂O₂ concentration, Fenton catalyst amount and irradiation time were assessed. According to the oxidation of phenol, it has been found that the oxidation by Fenton's reagent is dependent on the pH, contrary to the microwave system, which is not influenced by this parameter. For both systems, a limiting amount of oxidant has been found; above this point the oxidation of phenol is not improved by a further addition of peroxide. The oxidation of the industrial surfactant effluent has only been successful with the Fenton's reagent. In this case, large amounts of ferrous ions are necessary for the precipitation of the ionic surfactants of the effluent, followed by the oxidation of the non-ionic constituents of the solution. Electronic Publication