Assembly of the highest connectivity Wells-Dawson polyoxometalate coordination polymer: the use of organic ligand flexibility

Through tuning the length of flexible bis(triazole) ligands and different metal ion coordination geometries, four Wells-Dawson polyoxoanion-based hybrid compounds, [Cu-6(btp)(3)(P2W18O62)] center dot 3H(2)O (1) (btp = 1,3-bis(1,2,4-triazol-1-yl)propane), [Cu-6(btb)(3)((P2W18O62) center dot 2H(2)O (2), [Cu-3(btb)(6)(P2W18O62)] center dot 6H(2)O (btb = 1,4-bis(1,2,4-triazol-1-yl)butane) (3), and [Cu-3(btx)(5.5)((P2W18O62) center dot 4H(2)O (btx = 1,6-bis(1,2,4-triazol-1-yl)hexane) (4), were synthesized and structurally characterized. in compound 1, the metal-organic motif exhibits a ladder-like chain, which is further fused by the ennead-dentate [P2W18O62](6-) anions to construct a 3D structure. In compound 2, the metal-organic motif exhibits an interesting Cu-btb grid layer, and the ennead-dentate polyoxoanions are sandwiched by two Cu-btb layers to construct a 3D structure

Magnesium-Based 3D Metal-Organic Framework Exhibiting Hydrogen-Sorption Hysteresis

A new magnesium metal-organic framework (MOF) based on an asymmetrical ligand, biphenyl-3,4',5-tricarboxylate (H3PT) has been synthesized and structurally characterized. MOF Mg-3(BPT)(2)(H2O)(4) (1) consists of 10 hexagonal nanotube-like channels and exhibits pronounced hydrogen-sorption hysteresis at medium pressure.

Biomolecule-nanoparticle hybrids for electrochemical biosensors

Inorganic nanoparticles (NPs) with attractive electronic, optical, magnetic, thermal and catalytic properties have attracted great interest due to their important applications in physics, chemistry, biology, medicine, materials science and interdisciplinary fields. Biomolecule-NP hybrid systems, which combine recognition and catalytic properties of biomolecules with electronic, optical, magnetic and catalytic properties of NPs, are particularly new materials with synergistic properties originating from the components of the hybrid composites. The biomolecule-NP hybrid system has excellent prospects for interfacing biological recognition events with electronic signal transduction so as to design a new generation of bioelectronic devices with high sensitivity.

Water-resistant conducting hybrids from electrostatic interactions

Conductive hybrids were prepared in a water/ethanol solution via the Solgel process from an inorganic sol containing carboxyl groups and water-borne conductive polyaniline (cPANI). The inorganic sol was prepared by the hydrolysis and condensation of methyltriethoxysilane with the condensed product of maleic anhydride and aminopropyltriethoxysilane as a catalyst, for which the carboxyl counterion along the cPANI backbone acted as an electrostatic-interaction moiety. The existence of this electrostatic interaction could improve the compatibility of the two components and contribute to the homogeneous dispersion of cPANI in the silica phase. The electrostaticinteraction hybrids displayed a conductivity percolation threshold as low as 1.1 wt % polyaniline in an emeraldine base, showing 2 orders of magnitude higher electrical conductivity than that without electrostatic interactions. The electrostatic-interaction hybrids also showed good water resistance; the electrical conductivity with a cPANI loading of 16 wt % underwent a slight change after 14 days of soaking in water.

Confining conducting polyaniline in a stable inorganic network

Water soluble conducting polyaniline with electrical conductivity of 10(-1)-10(-2) S/cm was prepared employing dopant induced water solubility technology. The water resistance of the conducting film was significantly improved employing,sol-gel hybrids method, especially when the conductive polyaniline loading was below 30 wt%. The reason for the improvement is that the conducting polyaniline chains are confined in a stable inorganic network.

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.

Forms and functions of inorganic carbon in the Jiaozhou Bay sediments

Inorganic carbon forms and their influencing factors, mutual transformation and contribution to carbon cycling in the Jiaozhou Bay sediments were discussed. The results show that inorganic carbon in sediments could be divided into five forms: NaCl form, NH3 center dot H2O form, NaOH form, NH2OH center dot HCl form and HCl form. Thereinto, NH2OH center dot HCl form and HCl form account for more than 70% of total inorganic carbon. There was close relationship among every form of inorganic carbon and their correlativity was clearly different with different sedimentary environment except the similar strong positive correlation among NH2OH center dot HCl form, HCl form and total inorganic carbon in all regions of the Jiaozhou Bay. All forms of inorganic carbon were influenced by organic carbon, pH, Eh, Es, nitrogen and phosphorus in sediments, but their influence had different characteristics in different regions. Every farm of inorganic carbon transformed into each other continuously during early diagenesis of sediments and the common phenomenon was that NaCl form, NH3 center dot H2O form, NaOH form and NH2OH center dot HCl form might transform into steady HCl form. NaCl form, NH3 center dot H2O form, NaOH form and NH2OH center dot HCl form could participate in carbon recycle and they are potential carbon source; HCl form may be buried for a long time in sediments, and it may be one of the final resting places of atmospheric CO2. Inorganic carbon which entered into sediments was about 4.98 x 10(10) g in the Jiaozhou Bay every year, in which about 1.47x10(10) g of inorganic carbon might be buried for a long time and about 3.51. x 10(10) g of inorganic carbon might return into seawater and take part in carbon recycling.

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.

Inorganic carbon of sediments in the Yangtze River Estuary and Jiaozhou Bay

JGOFS results showed that the ocean is a major sink for the increasing atmospheric carbon dioxide resulting from human activity. However, the role of the coastal seas in the global carbon cycling is poorly understood. In the present work, the inorganic carbon (IC) in the Yangtze River Estuary and Jiaozhou Bay are studied as examples of offshore sediments. Sequential extraction was used to divide inorganic carbon in the sediments into five forms, NaCl form, NH3 H2O form, NaOH form, NH2OH HCl form and HCl form. Studied of their content and influencing factors were also showed that NaCl form < NH3 H2O form < NaOH form < NH2OH HCl form < HCl form, and that their influencing factors of pH, Eh, Es, water content, organic carbon, organic nitrogen, inorganic nitrogen, organic phosphorus and inorganic phosphorus on inorganic carbon can be divided into two groups, and that every factor has different influence on different form or on the same form in different environment. Different IC form may transform into each other in the early diagenetic process of sediment, but NaCl form, NH3 H2O form, NaOH form and NH2OH HCl form may convert to HCl form ultimately. So every IC form has different contribution to carbon cycling. This study showed that the contribution of various form of IC to the carbon cycle is in the order of NaOH form > NH2OH HCl form > NH3 H2O form > NaCl form > HCl form, and that the contribution of HCl form contributes little to carbon cycling, HCl form may be one of end-result of atmospheric CO2. So Yangtze River estuary sediment may absorb at least about 40.96x10(11) g atmospheric CO2 every year, which indicated that offshore sediment play an important role in absorbing atmospheric CO2.