Bioorganic/inorganic hybrid composition of sponge spicules: Matrix of the giant spicules and of the comitalia of the deep sea hexactinellid Monorhaphis

The giant basal spicules of the siliceous sponges Monorhaphis chuni and Monorhaphis intermedia (Hexactinellida) represent the largest biosilica structures on earth (up to 3 m long). Here we describe the construction (lamellar organization) of these spicules and of the comitalia and highlight their organic matrix in order to understand their mechanical properties. The spicules display three distinct regions built of biosilica: (i) the outer lamellar zone (radius: >300 mu m), (ii) the bulky axial cylinder (radius: <75 mu m), and (iii) the central axial canal (diameter: <2 mu m) with its organic axial filament. The spicules are loosely covered with a collagen net which is regularly perforated by 7-10 mu m large holes; the net can be silicified. The silica layers forming the lamellar zone are approximate to 5 mu m thick; the central axial cylinder appears to be composed of almost solid silica which becomes porous after etching with hydrofluoric acid (HF). Dissolution of a complete spicule discloses its complex structure with distinct lamellae in the outer zone (lamellar coating) and a more resistant central part (axial barrel). Rapidly after the release of the organic coating from the lamellar zone the protein layers disintegrate to form irregular clumps/aggregates. In contrast, the proteinaceous axial barrel, hidden in the siliceous axial cylinder, is set up by rope-like filaments. Biochemical analysis revealed that the (dominant) molecule of the lamellar coating is a 27-kDa protein which displays catalytic, proteolytic activity. High resolution electron microscopic analysis showed that this protein is arranged within the lamellae and stabilizes these surfaces by palisade-like pillars. The mechanical behavior of the spicules was analyzed by a 3-point bending assay, coupled with scanning electron microscopy. The load-extension curve of the spicule shows a biphasic breakage/cracking pattern. The outer lamellar zone cracks in several distinct steps showing high resistance in concert with comparably low elasticity, while the axial cylinder breaks with high elasticity and lower stiffness. The complex bioorganic/inorganic hybrid composition and structure of the Monorhaphis spicules might provide the blueprint for the synthesis of bio-inspired material, with unusual mechanical properties (strength, stiffness) without losing the exceptional properties of optical transmission. (C) 2007 Elsevier Inc. All rights reserved.

Matrix-bound phosphine: A new form of phosphorus found in sediment of Jiaozhou Bay

Matrix-bound phosphine (PH3), a new form of phosphorus, was found in sediment of Jiaozhou Bay in December 2001. Concentration and distribution of PH3 in different layers of sediment with different stations were analyzed. The results show that PH3 concentrations are various with different layers and different stations. PH3 concentrations in the bottom layer of sediment (20-30 cm) are usually higher than those in the surface layer (0-4 cm). The highest PH3 concentration in our investigation reaches 685 ng/kg (dry), which is much higher than those in terrestrial paddy soil, marsh and landfill that have been reported up to now. The correlation analysis indicates that there is no apparent correlation between the concentrations of PH3 and inorganic phosphorus in sediment. However, the correlation between the concentrations of phosphine and organic phosphorus in the bottom layer of sediment is remarkable (R-2=0.83). It is mainly considered that PH3 in sediment of Jiaozhou Bay is produced from the decomposition of organic phosphorus in the anaerobic condition, and so PH3 concentrations are related to organic phosphorus concentration and anaerobic environment in sediment. The discovery of PH3 in sediment will give people some new ideas on the mechanisms of phosphorus supplement and biogeochemical cycle in Jiaozhou Bay.

Distribution characteristics of matrix-bound phosphine along the coast of China and possible environmental controls

Matrix-bound phosphine (MBP) concentrations in surface sediments collected from 37 stations along the coast of China in 2006 are reported. MBP was found in all samples and the average concentration was 6.30 ng kg(-1) dry weight (dw). The distribution of MBP showed certain spatial variation characteristics with high MBP concentrations at stations near to the coast. The average concentrations of MBP in the northern Yellow Sea (NYS), the southern Yellow Sea (SYS), the northern area of East China Sea (NECS), the southern area of East China Sea (SECS), and South China Sea (SCS) were 5.57 +/- 3.78, 3.78 +/- 2.81, 5.27 +/- 3.07, 5.48 +/- 4.05 and 13.52 +/- 7.86 ng kg(-1) dw. respectively. The correlations between MBP and influencing factors, such as the sedimentary environmental characteristics (sediment type, the grain size, contents of phosphorous, organic matters and redox potential) and the aquatic environmental characteristics (temperature, salinity, depth and hydrodynamics) were studied. The results indicated that MBP was strongly influenced by various factors, such as total phosphorus (TP), organic phosphorus (OP), organic carbon (OC), the grain size and hydrodynamics, all of which not only offered reasonable interpretations for the distribution characteristics of MBP but also provided evidence to support the viewpoint that phosphine originated from OP decomposition. This work is the first comprehensive study of the distribution of MBP along the coast of China and its relationships with environmental factors which will lead to a better understanding of the phosphorus (P) biogeochemical cycle in the sea. (C) 2008 Elsevier Ltd. All rights reserved.

Seasonal and spatial distribution of matrix-bound phosphine and its relationship with the environment in the Changjiang River Estuary, China

Sediment is commonly considered as a source of phosphine, which is a highly toxic and reactive atmospheric trace gas. This study aims to investigate the seasonal and spatial distribution of matrix-bound phosphine (MBP) and its relationship with the environment in the Changjiang River Estuary. A total of 43 surface sediments were collected in four seasons of 2006, and concentrations of MBP and relative environmental factors were analyzed. MBP ranged from 1.93 to 94.86 ng kg(-1) dry weight (dw) with an average concentration of 17.14 ng kg(-1) dw. The concentrations of MBP in the tipper estuary were, higher than those in the lower estuary, which could be attributed to greater pollutant inputs in the upper estuary. The concentrations of MBP also varied with season, with November > August > May > February. Significant correlations existed between MBP and total phosphorus (TP), organic phosphorus (OP), inorganic phosphorus (W), organic carbon (OC), total nitrogen (TN), the grain size, and redox potential (Eh), suggesting that these sedimentary environmental characteristics played an important role in controlling the MBP levels in the sediments. Notably, there were positive linear relationships between the concentrations of soluble reactive phosphorus (SRP), TP, and chlorophyll a (Chl a) in bottom water and MBP in sediments. These relationships might be very complicated and need further exploration. This work is the first comprehensive study of the seasonal and spatial distribution of MBP in sediments and its relationships with environmental factors in a typical estuary, and will lead to deeper understanding of the phosphorus (P) biogeochemical cycle. (C) 2008 Elsevier Ltd. All rights reserved.

Three dimensional fluorescence excitation-emission on matrix spectrum of dissolved organic substance in marine microalgaes growth process

The three-dimensional fluorescence spectrum was used to detect the changes in dissolved organic substances from the cultured Skeletonema costatum, Alexandrium tamarense, Alexandrium mimutum, Scrippsiella trochodea, Prorocentrum donghaiense and Prorocentrum micans. The result indicates that all of the microalgaes can produce FDOM in the growth courses. Diatom such as Skeletonema costatum can produce humic-like FDOM. However dinoflagellate can produce protein-like FDOM at exponential growth phase. When the algae grows into decadency phase, the intensity of humic-like and protein-like fluorescence augments rapidly, which may be due to a mass of FDOM realeased by the old or dead cell fragmentation and the degradation of bacteria by using non-FDOM. The fluorescent intensity of Alexandrium tamarense, Alexandrium mimutum, Prorocentrum donghaiense and Prorocentrum micans can reduce at anaphase of decadency phase because of the degradation of bacteria and light. The same genus of algae can produce similar FDOM, for example: Alexandrium tamarense, and Alexandrium mimutum, Prorocentrum donghaiense and Prorocentrum micans, but the positions of the fluorescence peaks are different.

A study on the dependence of the micro-pore configurations on the volatilization and the burn processes of the organic compounds in the matrix of molten carbonate fuel cells

The micro-pore configurations on the matrix surface were studied by SEM. The matrix of molten carbonate fuel cell (MCFC) performance was also improved by the better coordination between the reasonable radius of the micro-pores and the higher porosity of the cell matrix. The many and complicated micro-pore configurations in the cell matrix promoted the volatilization of the organic additives and the burn of polyvinyl butyral (PVB). The smooth volatilization of the organic additives and the complete burn of PVB were the significant factors for the improved MCFC performance. Oxygen diffusion controlled-burn mechanism of PVB in the cell matrix was proposed. (C) 2002 Published by Elsevier Science Ltd.

Tensor density matrix theory for determining population and alignment of symmetric top molecule using rotationally unresolved fluorescence

General expressions used for transforming raw laser-induced fluorescence (LIF) intensity into the population and alignment parameters of a symmetric top molecule are derived by employing the density matrix approach. The molecular population and alignment are described by molecular state multipoles. The results are presented for a general excitation-detection geometry and then applied to some special geometries. In general cases, the LIF intensity is a complex function of the initial molecular state multipoles, the dynamic factors and the excitation-detection geometrical factors. It contains a population and 14 alignment multipoles. How to extract all initial state multipoles from the rotationally unresolved emission LIF intensity is discussed in detail.

Carbon nanotubes as adsorbent of solid-phase extraction and matrix for laser desorption/ionization mass spectrometry

A method with carbon nanotubes functioning both as the adsorbent of solid-phase extraction (SPE) and the matrix for matrix assisted laser desorption/ ionization mass spectrometry (MALDI-MS) to analyze small molecules in solution has been developed. In this method, 10 muL suspensions of carbon nanotubes in 50% (vol/vol) methanol were added to the sample solution to extract analytes onto surface of carbon nanotubes because of their dramatic hydrophobicity. Carbon nanotubes in solution are deposited onto the bottom of tube with centrifugation. After removing the supernatant fluid, carbon nanotubes are suspended again with dispersant and pipetted directly onto the sample target of the MALDI-MS to perform a mass spectrometric analysis. It was demonstrated by analysis of a variety of small molecules that the resolution of peaks and the efficiency of desorption/ ionization on the carbon nanotubes are better than those on the activated carbon. It is found that with the addition of glycerol and sucrose to the dispersant, the intensity, the ratio of signal to noise (S/N), and the resolution of peaks for analytes by mass spectrometry increased greatly. Compared with the previously reported method by depositing sample solution onto thin layer of carbon nanotubes, it is observed that the detection limit for analytes can be enhanced about 10 to 100 times due to solid-phase extraction of analytes in solution by carbon nanotubes. An acceptable result of simultaneously quantitative analysis of three analytes in solution has been achieved. The application in determining drugs spiked into urine has also been realized. (C) 2004 American Society for Mass Spectrometry.