STUDIES ON ORGANOLANTHANIDE COMPLEXES .56. FORMATION OF ION-PAIR COMPLEXES [NA.3PHEN]+[LN(C5H5)3CL]-.PHEN (LN=LA, PR OR ND, PHEN = 1,10-PHENANTHROLINE) AND CRYSTAL-STRUCTURE FOR LN=PR

In the presence of 1,10-phenanthroline (phen), lanthanide chlorides LnCl3 reacted with cyclopentadienylsodium to give the novel complexes [Na.3phen]+[Ln(C5H5)3Cl]-.phen (Ln = La, Pr or Nd). In the praseodymium case, crystal structure analysis showed that

ELECTROCHEMICAL FORMATION OF NI-Y INTERMETALLIC COMPOUND LAYER IN MOLTEN CHLORIDE

The reduction of Y(III) ions in molten chloride is known to be a one-step three electron reaction [1, 2, 3], but a voltammogram of YCl3 in molten LiCl-KCl-NaCl at a nickel electrode shows at least two reduction peaks of Y(III) ions, indicating the possibility of formation of Ni-Y intermetallic compounds. Using a galvanostatic electrolysis method, samples were prepared at several current densities at 450, 500, 600 and 700-degrees-C, respectively, and were identified with X-ray diffraction (XRD) and electron probe microanalysis (EPMA) methods. The results show that Ni2Y, Ni2Y3 and NiY can be produced by electrolysis and Ni2Y is found to be the predominant Ni-Y intermetallic compound under the experimental conditions. Nickel appears to diffuse in Ni2Y faster than yttrium, and the diffusion process is the rate determining step during Ni2Y formation.

MONOLAYER FORMATION OF A NOVEL AMPHIPHILIC POLYMER PAMC16S

Poly(2-acrylamido-hexadecylsulfonic acid) (PAMC16S) forms a stable monolayer on a pure water surface. More closely packed monolayers can be obtained when the subphase contains Cd2+ or Ca2+. Self-assembled monolayers have been formed on gold surfaces and characterized by contact angle measurement, XPS and electrochemical analysis. The results show that the monolayers are hydrophobic with the hydrophilic sulfonic acid groups adjacent to the metal surfaces and with the hydrocarbon chains extended from the surfaces. The monolayers exhibit great adsorption stability during the faradaic reactions, illustrating the advantage of polymeric LB films in potential applications.

Extra- and intra-cellular ice formation of red seabream (Pagrus major) embryos at different cooling rates

The ice crystal formation is assumed as the most lethal factor for the failure of fish embryo cryopreservation and intracellular ice formation (IIF) plays a central role in cell injury during cooling. The objectives were to observe the morphological changes of red seabream (Pagrus major) embryo during the cooling-thawing process, and to examine the effect of cryoprotectant and cooling rate on the temperatures of oil globule ice formation (T-OIF), extra-cellular ice formation (T-EIF) and intracellular ice formation (T-IIF) using cryomicroscope. After thawing, the morphological changes of embryos were observed and recorded by the video attachment and monitor under the microscope. During the cooling process, three representative phenomena were observed: oil globule gradually turned bright firstly, then the whole field of view flashed and the embryo blackened. Cooling rate affect the temperature of both extra- and intra-cellular ice formations. T-EIF and T-IIF at high cooling rate were much lower than that at low cooling rate. And the value of T-EIF - T-IIF increased from 0.45 to 11.11 degrees C with the increase of cooling rate from 3 to 130 degrees C/min. Taken together, our results suggested that high cooling rate with proper cryoprotectant would be a good option for red seabream embryo cryopreservation. (C) 2009 Elsevier Inc. All rights reserved.

Axial growth of hexactinellid spicules: Formation of cone-like structural units in the giant basal spicules of the hexactinellid Monorhaphis

The glass sponge Monorhaphis chuni (Porifera: Hexactinellida) forms the largest bio-silica structures on Earth; their giant basal spicules reach sizes of up to 3 m and diameters of 8.5 mm. Previously, it had been shown that the thickness growth proceeds by appositional layering of individual lamellae; however, the mechanism for the longitudinal growth remained unstudied. Now we show, that the surface of the spicules have towards the tip serrated relief structures that are consistent in size and form with the protrusions on the surface of the spicules. These protrusions fit into the collagen net that surrounds the spicules. The widths of the individual lamellae do not show a pronounced size tendency. The apical elongation of the spicule proceeds by piling up cone-like structural units formed from silica. As a support of the assumption that in the extracellular space silicatein(-like) molecules exist that associate with the external surface of the respective spicule immunogold electron microscopic analyses were performed. With the primmorph system from Suberites domuncula we show that silicatein(-like) molecules assemble as string- and net-like arrangements around the spicules. At their tips the silicatein(-like) molecules are initially stacked and at a later stay also organized into net-like structures. Silicatein(-like) molecules have been extracted from the giant basal spicule of Monorhaphis. Applying the SDS-PAGE technique it could be shown that silicatein molecules associate to dimers and trimers. Higher complexes (filaments) are formed from silicatein(-like) molecules, as can be visualized by electron microscopy (SEM). In the presence of ortho-silicate these filaments become covered with 30-60 nm long small rod-like/cuboid particles of silica. From these data we conclude that the apical elongation of the spicules of Monorhaphis proceeds by piling up cone-like silica structural units, whose synthesis is mediated by silicatein(-like) molecules. (C) 2008 Elsevier Inc. All rights reserved.

Formation of Fe-oxyhydroxides from the East Pacific Rise near latitude 13 degrees N: Evidence from mineralogical and geochemical data

The mineralogical and geochemical characteristics of Fe-oxyhydroxide samples from one dredge station (long. 103 degrees 54.48'W, lat. 12 degrees 42.30'N, water depth 2655 m) on the East Pacific Rise near lat 13 degrees N were analyzed by XRD, ICP-AES, and ICP-MS. Most Fe-oxyhydroxides are amorphous, with a few sphalerite microlites. In comparison with Fe-oxyhydroxides from other fields, the variable ranges in the chemical composition of Fe-oxyhydroxide samples are very narrow; their Fe, Si, and Mn contents were 39.90%, 8.92%, and 1.59%, respectively; they have high Cu (0.88%-1.85%) and Co (65x10(-6)-704x10(-6)) contents, and contain Co+Cu+Zn+Ni > 1.01%. The trace-element (As, Co, Ni, Cu, Zn, Ba, Sr) and major-element (Fe, Ca, Al, Mg) contents of these samples are in the range of hydrothermal sulfide from the East Pacific Rise near 13 degrees N, reflecting that this type of Fe-oxyhydroxide constitutes a secondary oxidation product of hydrothermal sulfide. The Fe-oxyhydroxide samples from one dredge station on the East Pacific Rise near 13 degrees N are lower in Sigma REE (5.44x10(-6)-17.01x10(-6)), with a distinct negative Ce anomaly (0.12-0.28). The Fe-oxyhydroxide samples have similar chondrite-normalized rare-earth-element (REE) patterns to that of seawater, and they are very different from the REE composition characteristics of hydrothermal plume particles and hydrothermal fluids, showing that the REEs of Fe-oxyhydroxide are a major constituent of seawater and that the Fe-oxyhydroxides can become a sink of REE from seawater. The quick settling of hydrothermal plume particles resulted in the lower REE content and higher Mn content of these Fe-oxyhydroxides, which are captured in part of the V and P from seawater by adsorption. The Fe-oxyhydroxides from one dredge station on the East Pacific Rise near 13 degrees N were formed by secondary oxidation in a low temperature, oxygenated environment. In comparison with the elemental (Zn, Cd, Pb, Fe, Co, Cu) average content of hydrothermal sulfide samples from the East Pacific Rise near 13 degrees N, the Zn, Cd, and Pb contents of the Fe-oxyhydroxides are lower, and their Fe, Co, and Cu contents are higher.

Bacterial roles in the formation of high-molecular-weight dissolved organic matter in estuarine and coastal waters: Evidence from lipids and the compound-specific isotopic ratios

High-molecular-weight dissolved organic matter (HMW-DOM, > 1,000 Daltons) is actively involved in the global biogeochemical cycling of many elements, but its carbon sources and detailed formation pathways are still not well understood. In this study, we measured bulk stable carbon and nitrogen isotopic ratios, lipid composition, and compound-specific carbon isotopic ratios of HMW-DOM samples collected from four U.S. estuaries (Boston Harbor/Massachusetts Bay, Delaware/Chesapeake Bay, San Diego Bay, and San Francisco Bay). Analytical results show (1) a fraction of HMW-DOM (lipid associated) in estuarine and coastal waters is derived from bacteria and phytoplankton; (2) this fraction of HMW-DOM is formed by various release processes of bacterial membrane components and bacterial reworking of phytoplankton-derived material; (3) this fraction of HMW-DOM is generally present in all samples from different coastal systems despite variable organic matter inputs and environmental conditions, suggesting an important bacterial role in HMW-DOM formation.

Is inorganic nutrient enrichment a driving force for the formation of red tides? A case study of the dinoflagellate Scrippsiella trochoidea in an embayment

Red tides (high biomass phytoplankton blooms) have frequently occurred in Hong Kong waters, but most red tides occurred in waters which are not very eutrophic. For example, Port Shelter, a semi-enclosed bay in the northeast of Hong Kong, is one of hot spots for red tides. Concentrations of ambient inorganic nutrients (e.g. N, P), are not high enough to form the high biomass of chlorophyll a (chl a) in a red tide when chl a is converted to its particulate organic nutrient (N) (which should equal the inorganic nutrient, N). When a red tide of the dinoflagellate Scrippsiella trochoidea occurred in the bay, we found that the red tide patch along the shore had a high cell density of 15,000 cells ml(-1), and high chl a (56 mu g l(-1)), and pH reached 8.6 at the surface (8.2 at the bottom), indicating active photosynthesis in situ. Ambient inorganic nutrients (NO3, PO4, SiO4, and NH4) were all low in the waters and deep waters surrounding the red tide patch, suggesting that the nutrients were not high enough to support the high chl a >50 mu g l(-1) in the red tide. Nutrient addition experiments showed that the addition of all of the inorganic nutrients to a non-red-tide water sample containing low concentrations of Scrippsiella trochoidea did not produce cell density of Scrippsiella trochoidea as high as in the red tide patch, suggesting that nutrients were not an initializing factor for this red tide. During the incubation of the red tide water sample without any nutrient addition, the phytoplankton biomass decreased gradually over 9 days. However, with a N addition, the phytoplankton biomass increased steadily until day 7, which suggested that nitrogen addition was able to sustain the high biomass of the red tide for a week with and without nutrients. In contrast, the red tide in the bay disappeared on the sampling day when the wind direction changed. These results indicated that initiation, maintenance and disappearance of the dinoflagellate Scrippsiella trochoidea red tide in the bay were not directly driven by changes in nutrients. Therefore, how nutrients are linked to the formation of red tides in coastal waters need to be further examined, particularly in relation to dissolved organic nutrients. (C) 2008 Elsevier B.V. All rights reserved.

Formation of nano-crystalline corrosion products on Zn-Al alloy coating exposed to seawater

Hot dip Zn-Al alloy coating performs better than hot dip galvanized coating and 55% Al-Zn-Si coating as well with regard to general seawater corrosion protection. A characterization of the corrosion products on Zn-Al alloy coating immersed in dynamic aerated seawater has been performed mainly based on transmission electron microscopy (TEM) for morphological analysis and X-ray diffraction (XRD) technique for crystalline phase identification. The XRD and TEM analyses showed that the corrosion products mainly were typical nanometer Zn4CO3(OH)(6).H2O, Zn-5(OH)(8)Cl-2 and Zn6Al2CO3(OH)(16). 4H(2)O microcrystals. This probably is connected to the co-precipitation of Zn2+ and Al3+ ions caused by adsorption. Zn-Al alloy coating being suffered seawater attacks, AI(OH)(3) gel was first produced on the coating surface. Zn and Al hydroxides would co-precipitate and form double-hydroxide when the concentration of adsorbed Zn2+ ions by the newly produced gel exceeded the critical degree of supersaturation of the interphase nucleation. However, because the growth of the crystals was too low to keep in step with the nucleation, a layer of nano-crystalline corrosion products were produced on the surface of the coating finally. (C) 2001 Elsevier Science Ltd. All rights reserved.