Toxic Congener-Specific Analysis of PCBs: Assessment of Toxicity in Equivalents of TCDD

Abstract

High resolution capillary gas chromatographic analysis of the polychlorobiphenyls (PCBs) present in snapping turtle eggs, provided quantitative data on selected toxic congeners. The concentrations of these congeners have been converted into equivalent toxic concentrations of 2,3,7,8-tetrachloro-p-dibenzodioxin (TCDD). The toxic equivalent factors (TEFs), necessary to effect this transformation were derived from EC₅₀ values (half the concentration of the toxic congener required to produce the maximum effect) for aryl hydrocarbon hydroxylase (AHH) induction associated with the corresponding toxic PCB congener or isomer. Summation of the resulting toxic equivalents provided a composite assessment of the toxlcity of the PCB mixture in terms of an equivalent concentration of TCDD.     

Palladium(II) complexes bearing N‐alkylpiperidoimidazolin‐2‐ylidene derivatives: Effect of alkyl chain length of ligands on catalytic activity

A series of piperidoimidazolinium salts which differ in the chain lengths (butyl, octyl, dodecyl, octadecyl) and their Pd–N‐heterocyclic carbene complexes with pyridine were synthesized and characterized using elemental analysis and spectroscopic methods. The effects of these ligands on catalyst activation and the performance of the complexes were studied in Suzuki–Miyaura reactions of arylboronic acid with aryl chlorides. The complex with the ligand having the longest chain length was found to be most active. The results demonstrated that the length of the alkyl chain of the piperidoimidazolin‐2‐ylidene controlled the dispersion and composition of the nanoparticles and it affected the catalytic activity. The impact of alkyl chain length of piperidoimidazolin‐2‐ylidene on the Suzuki–Miyaura reactions of arylboronic acid with aryl halides was systematically investigated.     

Syntheses,structures, and properties of Ni(II) complexes with 5,5′-bis(4-halogenphenyl)diazo-dipyrromethane

Ni(II) complexes with 5,5′-bis(4-halogenphenyl)diazo-dipyrromethane have been synthesized and characterized by X-ray crystallography. All the complexes have similar crystal structures in which Ni(II) is square-planar by coordinating to two pyrrole and two azo nitrogen atoms. The azo-pyrroles of the ligands can be converted to the hydrazone tautomer after complexing nickel. Moreover, the C–H?···?Ni interaction played an important role in directing self-assembly of the complexes. The UV-Vis spectra of the complexes showed great difference with the metal complexes of pyrrol-2-imine.     

Separation of Xylene Isomers in the Anion-Pillared Square Grid Material SIFSIX-1-Cu

Xylene isomer separation is considered one of the seven separation challenges that changed the world. In addition, the high-energy demand of xylene separation highlights the need for efficient novel adsorbents. Herein, the liquid-phase separation potential of the anion-pillared hybrid material SIFSIX-1-Cu was studied for preferential adsorption of o-xylene and m-xylene over p-xylene, which was inspired by a previous complexation crystallization method for separating m-xylene. We report detailed experimental liquid-phase adsorption experiments, yielding selectivities of 3.0 for o-xylene versus p-xylene and 2.6 for m-xylene versus p-xylene. Our theoretical calculations thus provide a reasonable explanation that the xylene adsorption selectivity is attributed to the C−H⋅⋅⋅F interaction, and the host–guest interaction order agrees with the adsorption priority: o-xylene > m-xylene > p-xylene.     

ESSENTIALLY ALGEBRAIC CATEGORIES

Abstract

Various familiar concepts of algebraic categories (such as primitive and quasiprimitive categories of algebras as well as varietal, monadic, regular monadic, and regular categories) are contrasted with each other and with the new notion of essentially algebraic categories.

The new notion has pleasant features and covers several cases of an apparently algebraic nature, which are not covered by any of the older concepts.     

CuI heterogenized on thiosemicarbazide modified‐multi walled carbon nanotubes (thiosemicarbazide‐MWCNTs‐CuI): Novel heterogeneous and reusable nanocatalyst in the C‐N Ullmann coupling reactions

Herein we described the synthesis of novel thiosemicarbazide‐MWCNTs‐CuI nanocatalyst by covalent grafting of thiosemicarbazide on carbon nanotubes surface and subsequent coordination with CuI catalyst. The formation of nanocatalyst was analyzed by Raman spectroscopy, energy dispersive spectroscopy (EDS), wavelength‐dispersive X‐ray spectroscopy (WDX) and ICP analysis. The morphology of the nanocatalyst was characterized using scanning and transmission electron microscopes (SEM and TEM). Additionally, the (thiosemicarbazide‐MWCNTs‐CuI) nanocatalyst was successfully employed in the N ‐arylation of indole, amines and imidazoles through intermolecular C(aryl)‐N bond formation from the corresponding aryl halides (Ar–I, Ar–Br, Ar–Cl) with amines through Ullmann‐type coupling reactions. Interestingly, the novel catalyst could be recovered and recycled five times.     

直觉I-Fuzzy拓扑空间的杨忠道定理

以L~*-格值上Lukasiewicz蕴含算子为工具引入了直觉I-Fuzzy拓扑空间中导集概念,接着给出它的一些性质,最后证明了直觉I-Fuzzy拓扑空间中导集的杨忠道定理.     

Palladium nanoparticles deposited on a graphene–benzimidazole support as an efficient and recyclable catalyst for aqueous‐phase Suzuki–Miyaura coupling reaction

Graphene oxide was functionalized with benzimidazole for palladium immobilization. The resultant graphene–benzimidazole‐supported palladium composite (G‐BI‐Pd) was characterized using infrared and Raman spectroscopies, transmission electron microscopy and energy‐dispersive X‐ray spectroscopy. G‐BI‐Pd showed excellent catalytic activity and fast reaction kinetics in the aqueous‐phase Suzuki–Miyaura reaction of aryl iodides and bromides with phenylboronic acid under relatively mild conditions (5–25 min, 80 °C). The catalyst can be used several times without any significant loss of its catalytic activity.     

金属氧化物对十氯联苯的降解研究

分别以市售的Fe2O3、MgO和CaO为催化剂,对十氯联苯(CB209)进行了催化降解研究.结果表明,MgO对CB209的降解具有较高的活性.在反应温度为300℃,反应时间为60 min时,MgO对CB209的降解效率达到98.9%.进一步研究表明,MgO催化降解CB209的动力学符合准一级动力学反应.通过GC-MS和GC-ECD,并结合衍生化实验,检测到九氯联苯、五氯苯和四氯苯、五氯苯酚、四氯苯酚和三氯苯酚等降解产物,进而推测出MgO催化降解CB209的过程中存在相互竞争的反应路径:氧化反应、碳碳桥键断裂和加氢脱氯.