Studies of the ortho effect in fragmentations of acetyl ion adducts of disubstituted benzenes

The ion-molecule reactions of disubstituted benzenes under chemical ionization conditions with acetyl chloride as reagent gas were examined, and the fragmentation reactions of the adduct ions (mostly proton and acetyl ion adducts) were studied by collision-induced dissociation. Electron-releasing substituents favored the adduct reactions, and electron-withdrawing groups did not. The position and properties of substituting groups had an effect on the relative abundances of the adduct ions. Several examples of the ortho effect were observed. The fragmentation reaction of the adduct ions formed by ortho-benzenediamine with the acetyl ion was similar to the reductive alkylation reaction of amines in the condensed phase. Copyright (C) 2001 John Wiley & Sons, Ltd.

Theoretical study on the mechanisms of some elementary reactions catalyzed by modified carbonyl cobalt

All structural geometries of intermediates, transition states and product are, optimized at HF/ LANL2DZ level under the effective core potential approximation. The potential energy profile for some elementary reactions of hydroformylation catalyzed by Co-2(CO)(6)(PH3)(2), consisting of carbonyl insertion, H-2 oxidative addition and aldehyde reductive elimination, are calculated, The transition states are further confirmed by having one and only one imaginary vibrational frequency, The activation energies of carbonyl insertion, H-2 oxidative addition and aldehyde reductive elimination are 54, 02, 134, 02 and 43. 44 kJ/mol, respectively.

ELECTROCHEMICAL DETECTION OF COBALT IN HAIR FOLLOWING ON-COLUMN DERIVATIZATION WITH 1-(2-PYRIDYLAZO)-2-NAPHTHOL-6-SULFONIC ACID AND REVERSED-PHASE LIQUID-CHROMATOGRAPHY

A method for the specific determination of cobalt based on reversed-phase liquid chromatography with amperometric detection via on-column complex formation has been developed. A water-soluble chelating agent, 1-(2-pyridylazo)-2-naphthol-6-sulphonic acid (PAN-6S), is added to the mobile phase and aqueous cobalt solutions are injected directly into the column to form in situ the cobalt-PAN-6S chelate, which is then separated from other metal PAN-6S chelates and subjected to reductive amperometric detection at a moderate potential of -0.3 V. Because the procedure eliminates the interference of oxygen and depresses the electrochemical reduction of the mobile phase-containing ligand PAN-6S, by virtue of the quasi:reversible electrode process of the cobalt-PAN-6S complex, a low detection limit of 0.06 ng can be readily obtained. Interference effects were examined for sixteen common metal species, and at a 5- to 8000-fold excess by mass no obvious interference was observed. The feasibility of the method as an approach to the specific analysis of cobalt in a hair sample has been demonstrated.

THE REVERSIBLE ELECTRON-TRANSFER REACTION OF MYOGLOBIN AT BRILLIANT CRESYL BLUE MODIFIED PLATINUM GAUZE ELECTRODE

The electrochemical behavior of myoglobin at a Brilliant Cresyl Blue (BCB) modified platinum gauze electrode and spiral pt wire in the BCB solution in optically transparent thin layer cell base been investigated by using cyclic potential-absorbance method and double potential step chronoabsorptometry. The results reveal a reversible electron transfer resection of myoglobin. Exhaustive reductive and oxidative electrolyses are achieved at the modified platinum surface in 20 and 100s respectively. The formal h...

Sedimentary changes during the Holocene in the Bohai Sea and its paleoenvironmental implication

Samples of two cores, Cores M5-5 and M7-4 in the Bohai Sea were analyzed in isotopes, grain size, heavy minerals, chemical compositions, and 14 C dating to reconstruct the sedimentation during the Holocene. Abrupt change in carbon and oxygen stable isotopes was recognized at Core M5-5 at about 6400 a BP, which was likely due to the intrusion of the Yellow Sea Warm Current (YSWC) extension into the Bohai Sea. At Core M7-4, sediments between 5900 and 6600 a BP (150-260 cm depth) became coarse-grained, containing rich garnet, high manganese content, and nil autogenic pyrite, indicating a very dynamic sedimentary event during which the ambience was transformed from reductive to oxidative, and sedimentation boosted. Meanwhile, the YSWC had invaded into the Bohai Sea indicated by rich planktonic foraminifera in this event. (c) 2008 Elsevier Ltd. All rights reserved.

In vitro determination of antioxidant activity of proteins from jellyfish Rhopilema esculentum

In this study, the antioxidant activity of proteins isolated from jellyfish, Rhopilema esculentum Kishinouye (R. esculentum), was determined by various antioxidant assays, including superoxide anion radical-scavenging, hydroxyl radical-scavenging, total antioxidant activity, reducing power and metal chelating activity. Butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), alpha-tocopherol, vitamin C and mannitol were used as standards in those various antioxidant activities. The crude protein (CP) and the protein fractions isolated by Sephadex chromatography, first peak (FP) and second peak (SP), had very low reductive power and metal chelating abilities compared to EDTA, but they showed strong scavenging effects on the superoxide anion radical, hydroxyl radical and varying total antioxidant activity. FP and SP exhibited stronger scavenging effects on the superoxide anion radical than BHA, BHT or a-tocopherol. The EC50 values of FP and SP were 6.12 and 0.88 mu g/ml, respectively, while values EC50 of BHA, BHT and alpha-tocopherol were 31, 61 and 88 mu g/ml, respectively. CP, FP and SP showed far higher hydroxyl radical-scavenging activities than did vitamin C or mannitol. The EC50 values of CP, FP and SP were 48.76, 45.42 and 1.52 mu g/ml, but EC50 values of vitamin C and mannitol were 1907 and 4536 mu g/ml, respectively. In a beta-carotene-linoleate system, SP and CP showed antioxidant activity, but lower than BHA. Of the three samples, SP had the strongest antioxidant activity. So, SP may have a use as a possible supplement in the food and pharmaceutical industries. (c) 2005 Elsevier Ltd. All rights reserved.

Effect of nano-TiO(2)on MP-25 resin

MP-25 resin is a chlorine-containing polymer widely used in coatings. The effects of two types of nano-TiO2 (P-25 and RM301 LP) on MP-25 were studied with saline immersion, UV irradiation, and electrochemical impedance spectroscopy. UV irradiation was evaluated in terms of gloss change and X-ray photoelectron spectroscopy (XPS). The results indicate that, compared to pigment R-930 TiO2, P-25 reduced the immersion resistance and accelerated UV aging of the MP-25 coating, whereas RM301 LP showed the opposite effects. XPS analysis showed that MP-25 resin degraded under UV irradiation via dechlorination and C-C bond breakage, similarly to poly(vinyl chloride), but RM301 LP could inhibit the aging of MP-25 to a certain extent. A skin effect of oxygen and chlorine was identified in MP-25 resin by XPS. RM301 LP could improve the impedance of the MP-25 coating because of its excellent fill capacity. Hence, rutile nano-TiO2 RM301 LP represents an excellent additive for MP-25 resin. (c) 2007 Wiley Periodicals, Inc.

黄东海及朝鲜海峡冰后期陆架沉积物的环境磁学研究

There are four chapters in this dissertation. The first chapter briefly synthesizes the basic theories, methods and present-day applying situation of environmental magnetism. The second chapter probes into the magnetic mineral diagenesis in the post-glacial muddy sediments from the southeastern South Yellow Sea and its response to marine environmental changes, using the muddy sediment of Core YSDP103 formed in the shelf since about 13 ka BP. The third chapter illustrates the high-resolution early diagenetic processes by investigating the rapidly deposited muddy sediments during the last 6 ka in Cores SSDP-102 and SSDP-103 from the near-shore shelf of Korea Strait. The fourth chapter presents the results of detailed rock magnetic investigation of the surface sediments from the fine-grained depositional area on the outer shelf of the East China Sea in an attempt to provide environmental magnetic evidence for the provenance of the fine-grained deposit. Core YSDP103 was retrieved in the muddy deposit under the cold eddy of the southeastern South Yellow Sea, and the uppermost 29.79 m core represents the muddy sediments formed in the shelf since about 13 ka BP. The lower part from 29.79 to 13.35 m, called Unit A2, was deposited during the period from the post-glacial transgression to the middle Holocene (at about 6 ~(14)C ka BP) when the rising sea level reached its maximum, while the upper part above 13.35 m (called Unit Al) was deposited in a cold eddy associated with the formation of the Yellow Sea Warm Current just after the peak of post-glacial sea level rise. For the the uppermost 29.79 m core, detailed investigation of rock-magnetic properties and analyses of grain sizes and geochemistry were made. The experimental results indicate that the magnetic mineralogy of the core is dominated by magnetite, maghemite and hematite and that, except for the uppermost 2.35 m, the magnetic minerals were subject to reductive diagenesis leading to significant decline of magnetic mineral content and the proportion of low-coercivity component. More importantly, ferrimagnetic iron sulphide (greigite) is found in Unit A2 but absent in Unit Al, suggesting the control of marine environmental conditions on the magnetic mineral diagenesis. Magnetic parameters show abrupt changes across the boundary between the Unit Al and A2, which reflects a co-effect of environmental conditions and primary magnetic components of the sediments on the diagenesis. Alternating zones of high and low magnetic parameters are observed in Unit A2 of Core YSDP103, which is presumably due to periodic changes of the concentration and/or grain size of magnetic minerals carried into the study area. Cores SSDP-102 and SSDP-103, two studied sediment cores from the Korea Strait contain mud sequences (14 m and 32.62 m in thickness) that were deposited during the last 6,000 years. Analyses of grain sizes and geochemistry of the cores have demonstrated that the sediments have uniform lithology and geochemical properties, however, marked down-core changes in magnetic properties suggest that diagenesis has significantly impacted the magnetic properties. An expanded view of early diagenetic reactions that affect magnetic mineral assemblages is evident in these rapidly deposited continental shelf sediments compared to deep-sea sediments. The studied sediments can be divided into four descending intervals, based on magnetic property variations. Interval 1 is least affected by diagenesis and has the highest concentrations of detrital magnetite and hematite, and the lowest solid-phase sulfur contents. Interval 2 is characterized by the presence of paramagnetic pyrite and sharply decreasing magnetite and hematite concentrations, which suggest active reductive dissolution of detrital magnetic minerals, the absolute minimum abundance of magnetite is reached at the end of this interval. Interval 3 is marked by a progressive loss of hematite with depth, and at the base of this interval, 82% to 88% of the hematite component was depleted and the bulk magnetic mineral concentration was reduced to the lowest value in the entire studied mud section. Interval 4 has an increasing down-core enhancement of authigenic greigite, which is interpreted to have formed due to arrested pyritization resulting from consumption of pore water sulfate with depth. This is the first clear demonstration from an active depositional environment for a delay of thousands of years for acquisition of a magnetization carried by greigite. This detailed view of diagenetic processes in continental shelf sediments suggests that studies of geomagnetic field behavior from such sediments should be conducted with care. Paleoceanographic and paleoclimatic studies based on the magnetic properties of shelf sediments with high sedimentation rates like those in the Korea Strait are also unlikely to provide a meaningful signature associated with syn-depositional environmental processes. The rock magnetic properties of the surface sediments from the fine-grained depositional area on the outer shelf of the East China Sea, an area surrounded by sands, are investigated with a view to providing information on the sediment provenance. Multiple magnetic parameters such as magnetic susceptibility (%), anhysteretic remanent magnetization (ARM), saturation rernanent magnetization (SIRM), coercivities of SIRM (Her), and S ratios (relative abundance of low-coercivity magnetic minerals) are measured for all 179 surface samples, and partial representative samples are examined for their magnetic hysteresis parameters, temperature-dependence of magnetic susceptibility and x-ray diffraction spectra. Our research indicates that the magnetic mineralogy is dominated by magnetite with a small amount of hematite and is primarily of pseudo-single domain (PSD) to multidomain (MD) nature with a detrital origin. In the surface sediments, the granulometry of magnetic fractions is basically independent of grain sizes of the sediment containing the magnetic grains, and the composition of magnetic minerals remains almost homogeneous, that is, with a relatively constant ratio of low to high coercivity fraction throughout the area. The magnetic concentration in the study area generally decreases to the east or southeast accompanied by magnetic-particle fining to the east or to the northeast. The geographic pattern of magnetic properties is most reasonably explained by a major source of sediment jointly from the erosion of the old Huanghe River deposit and the discharge of the Changjiang River. The rock magnetic data facilitate understanding of the transport mechanism of fine-grained sediments in the outer shelf of the East China Sea.

Highly efficient route to diselenides from the reactions of imines and selenium in the presence of carbon monoxide and water

Reactions of selenium with imines ((RRC)-C-1=NR2) of aldehydes and ketones in the presence of carbon monoxide, water and triethylamine lead to reductive selenation, on aerobic work-up, to afford symmetrical diselenides ((RRCHSe)-C-1)(2) in good to excellent yields. The proposed mechanism suggests that both in situ generated carbonyl selenide (SeCO) and hydrogen selenide (H2Se) are involved in the reaction.

A practical approach to the degradation of polychlorinated biphenyls in transformer oil

A practical and efficient disposal method for hydrodechlormation of polychlorinated biphenyls (PCBs) in transformer oil is reported. Transformer oil containing PCBs was treated by nanometric sodium hydride (nano-NaH) and transition metal catalysts. High destruction and removal efficiency (89.8%) can be attained by nano-NaH alone under mild conditions. The process exhibits apparent characteristics of a first order reaction. The reductive ability of nano-NaH was enhanced by the addition of transition metal catalysts. In the presence of TiCl4, 99.9% PCBs was hydrodechlorinated. The complex reducing reagents, Ni(OAc)(2) + i-PrONa, show extra hydrodechlorinating activity for di-chlorinated biphenyls. (c) 2004 Elsevier Ltd. All rights reserved.