Protein encapsulation and release from PEO-b-polyphosphoester templated calcium carbonate particles

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Influence of the type of phospholipid head and of the conformation of the polyelectrolyte on the growth of calcium carbonate thin films on LB/LbL matrices

Calcium carbonate is one of the most important biominerals, and it is the main constituent of pearls, seashells, and teeth. The in vitro crystallization of calcium carbonate using different organic matrices as templates has been reported. In this work, the growth of calcium carbonate thin films on special organic matrices consisting of layer-by-layer (LbL) polyelectrolyte films deposited on a pre-formed phospholipid Langmuir-Blodgett (LB) film has been studied. Two types of randomly coiled polyelectrolytes have been used: lambda-carrageenan and poly(acrylic acid). A precoating comprised of LB films has been prepared by employing a negatively charged phospholipid, the sodium salt of dimyristoilphosphatidyl acid (DMPA), or a zwitterionic phospholipid, namely dimyristoilphosphatidylethanolamine (DMPE). This approach resulted in the formation of particulate calcium carbonate continuous films with different morphologies, particle sizes, and roughness, as revealed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The crystalline structure of the calcium carbonate particles was analyzed by Raman spectroscopy. The randomly coiled conformation of the polyelectrolytes seems to be the main reason for the formation of continuous films rather than CaCO3 isolated crystals. (C) 2012 Elsevier B.V. All rights reserved.

Direct conversion of calcium carbonate to C-1-C-3 hydrocarbons

With the objective of investigating the direct conversion of inorganic carbonates such as CaCO3 to hydrocarbons, assisted by transition metal ions, we have carried out studies on CaCO3 in an intimate admixture with iron oxides (FeCaCO) with a wide range of Fe/Ca mole ratios (x), prepared by co-precipitation. The hydrogen reduction of FeCaCO at 673 K gives up to 23% yield of the hydrocarbons CH4, C2H4, C2H6 and C3H8, leaving solid iron residues in the form of iron metal, oxides and carbide particles. The yield of hydrocarbons increases with x and the conversion of hydrocarbons occurs through the formation of CO. While the total yield of hydrocarbons obtained by us is comparable to that in the Fischer-Tropsch synthesis, the selectivity for C-2-C-3 hydrocarbons reported here is noteworthy.

Composite cyclodextrin-calcium carbonate porous microparticles and modified multilayer capsules: novel carriers for encapsulation of hydrophobic drugs

Novel composite cyclodextrin (CD)-CaCO3 spherical porous microparticles have been synthesized through Ca2+-CD complex formation, which influences the crystal growth of CaCO3. The CDs are entrapped and distributed uniformly in the matrix of CaCO3 microparticles during crystallization. The hydrophobic fluorescent molecules coumarin and Nile red (NR) are efficiently encapsulated into these composite CD-CaCO3 porous particles through supramolecular inclusion complexation between entrapped CDs and hydrophobic molecules. Thermogravimetric (TGA) and infrared spectroscopy (IR) analysis of composite CD-CaCO3 particles reveals the presence of large CDs and their strong interaction with calcium carbonate nanoparticles. The resulting composite CD-CaCO3 microparticles are utilized as sacrificial templates for preparation of CD-modified layer-by-layer (LbL) capsules. After dissolution of the carbonate core, CDs are retained in the interior of the capsules in a network fashion and assist in the encapsulation of hydrophobic molecules. The efficient encapsulation of the hydrophobic fluorescent dye, coumarin, was successfully demonstrated using CD-modified capsules. In vitro release of the encapsulated coumarin from the CD-CaCO3 and CD-modified capsules has been demonstrated.

A Molecular Dynamics Study of the Early Stages of Calcium Carbonate Growth

The precipitation of calcium carbonate in water has been examined using a combination of molecular dynamics and umbrella sampling. During 20 ns molecular dynamics trajectories at elevated calcium carbonate concentrations, amorphous particles are observed to form and appear to be composed of misaligned domains of vaterite and aragonite. The addition of further calcium ions to these clusters is found to be energetically favorable and virtually barrierless. By contrast, there is a large barrier to the addition of calcium to small calcite crystals. Thus, even though calcite nanocrystals are stable in solution, at high supersaturations, particles of amorphous material form because this material grows much faster than ordered calcite nanocrystals.

Grain-size distribution, carbon and calcium carbonate at DSDP Leg 63 Holes

Sand-silt-clay distribution was determined at Scripps on samples collected at the time the cores were split and described. The sediment classification used here is that of Shepard (1954); sand, silt, and clay boundaries are determined on the basis of the Wentworth (1922) scale. Thus the sand, silt, and clay fractions are composed of particles whose diameters range from 2000 to 62.5 µm, 62.5 to 3.91 µm, and less than 3.91 µm, respectively. This classification is applied regardless of sediment type and origin.

Grain-size, carbona and calcium carbonate at DSDP Leg 58 Holes

Sand-silt-clay distribution was determined on 10-cm**3 sediment samples collected at the time the cores were split and described. The sediment classification used here is that of Shepard (1954), with the sand, silt, and clay boundaries based on the Wentworth (1922) scale. Thus the sand, silt, and clay fractions are composed of particles whose diameters are 2000 to 62.5 µm, 62.5 to 3.91 µm, and less than 3.91 µm, respectively. This classification is applied without regard to sediment type and origin; therefore, the sediment names used in this table may differ from those used elsewhere in this volume; e.g., a silt composed of nannofossils may be called a nannofossil ooze in a site chapter.

Index properties, calcium carbonate content and opal concentration of ODP Core 167-1016B-17H sediments

Physical properties measurements provide a relatively inexpensive and fast way to obtain high-resolution estimates of the variations in sedimentological properties. To better resolve the validity and cause of the geophysical signals measured by the Ocean Drilling Program (ODP) shipboard multisensor track (MST) instruments, 223 x 10 cm**3 core samples were collected at 4 cm intervals in Core 167-1016B-17H at the California Margin Conception Transect for the measurements of index properties, carbonate content, and opal content. This core was chosen because hole-to-hole stratigraphic correlation of MST data suggested that Core 17H corresponds to a depth interval that displays the greatest range of amplitude of many physical properties.

Calcium carbonate content and anisotropy of magnetic susceptibility of ODP Leg 172 sites

Sediments from Sites 1057 and 1061 of Ocean Drilling Program Leg 172 on the Blake Outer Ridge exhibit nearly isotropic magnetic susceptibility. Resolving the degree of anisotropy of magnetic susceptibility proved difficult in many samples because of the generally weak magnetic susceptibility of the sediments relative to the noise level of the susceptibility meters used. Lineation varies from 1.0 to 1.013 and foliation varies from 1.0 to 1.08 in the samples that pass rejection criteria. In general the foliation is better resolved than the lineation, particularly at Site 1061, where the foliation exhibits long-term trends that mimic the mean susceptibility. The changes in the foliation at this site are likely the result of changes in the magnetic mineralogy of the sediment. The poorly developed or absent magnetic fabric in the sediments overall can be attributed to high carbonate concentrations and to a circulation regime that was diffuse or with currents too weak to effectively align magnetic particles.

(Table 1) Calcium carbonate and <2 µm fractions of bulk sample and insoluble residue at DSDP Hole 92-597

Particles of red brown to yellow brown semiopaque oxides (RSO) dominate the insoluble residue fraction of the sediments at Site 597. Unlike the X-ray amorphous particles in the Bauer Deep sediments, these particles are composed of mainly goethite; the amount of X-ray amorphous ferric hydroxide and poorly crystalline ferromanganese oxyhydroxides is generally small relative to the amount of goethite. A qualitative goethite crystallinity index was established. The variations observed in the crystallinity of goethite with increasing depth and changes in lithology suggest that aging and long-term exposure to seawater in a high water/sediment regime influence and increase the rate of recrystallization of the Fe-oxyhydroxides of the RSO particles. The percentage of organic carbon is low in these sediments; it varies primarily between 0.2 and 0.4 wt.%. Phillipsite is present throughout the sediment column and is more concentrated in the youngest clay layer and in the oldest basal sediments.

Double hydrophilic polyphosphoester containing copolymers as efficient templating agents for calcium carbonate microparticles

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