Hydrophobic polycationic coatings disinfect poliovirus and rotavirus solutions.

Coating surfaces with N-alkylated polyethylenimines (PEIs), namely branched N,N-hexyl,methyl-PEI via covalent attachment to glass or linear N,N-dodecyl,methyl-PEI by physical deposition ("painting") onto polyethylene, enables the resultant materials to quickly and efficiently disinfect aqueous solutions of (non-enveloped) poliovirus and rotavirus.

Extracellular biosynthesis of magnetite using fungi.

The development of synthetic processes for oxide nanomaterials is an issue of considerable topical interest. While a number of chemical methods are available and are extensively used, the collaborations are often energy intensive and employ toxic chemicals. On the other hand, the synthesis of inorganic materials by biological systems is characterized by processes that occur at close to ambient temperatures and pressures, and at neutral pH (examples include magnetotactic bacteria, diatoms, and S-layer bacteria). Here we show that nanoparticulate magnetite may be produced at room temperature extracellularly by challenging the fungi, Fusarium oxysporum and Verticillium sp., with mixtures of ferric and ferrous salts. Extracellular hydrolysis of the anionic iron complexes by cationic proteins secreted by the fungi results in the room-temperature synthesis of crystalline magnetite particles that exhibit a signature of a ferrimagnetic transition with a negligible amount of spontaneous magnetization at low temperature.

Free-standing nanogold membranes as supports for the growth of calcium phosphate crystals.

Current strategies for bone tissue regeneration focus on the development of implantable matrices that mimic biological tissues. Inorganic composites are of special interest for bone substitute applications. It is necessary to create an artificial three-dimensional scaffold-like porous material with certain geometrical structure to induce bone growth. We report here the growth of calcium phosphate crystals on free-standing carboxylic acid functionalized gold nanoparticle membranes. The gold nanoparticle membrane is synthesized by the spontaneous reduction of aqueous chloroaurate ions by a diamine molecule at a liquid-liquid interface. This membrane is robust and malleable, and most importantly, the gold nanoparticles in the membrane may be functionalized with suitable ligands. In this study, the amino acids aspartic acid and cysteine together with an aromatic bifunctional molecule, anthranilic acid, were used to modify the surface of the gold nanoparticles in the membrane. The free carboxylic acid groups on the gold nanoparticles further to functionalization with these molecules were then used to bind Ca(2+) ions and reacted with phosphate ions to yield calcium phosphate. The nature of the nanogold surface modifier directed the formation of either crystalline hydroxyapatite or amorphous calcium phosphate. The nanogold membrane thus suggests potential biomedical application as biocompatible implants and grafts.

Heavy-metal remediation by a fungus as a means of production of lead and cadmium carbonate crystals.

We show here that reaction of the fungus, Fusarium oxysporum, with the aqueous heavy-metal ions Pb2+ and Cd2+ results in the one-step formation of the corresponding metal carbonates. The metal carbonates are formed by reaction of the heavy-metal ions with CO2 produced by the fungus during metabolism and thus provide a completely biological method for production of crystals of metal carbonates. The PbCO3 and CdCO3 crystals thus produced have interesting morphologies that are shown to arise because of interaction of the growing crystals with specific proteins secreted by the fungus during reaction. An additional advantage of this approach is that the reaction leads to detoxification of the aqueous solution and could have immense potential for bioremediation of heavy metals. Under conditions of this study, the metal ions are not toxic to the fungus, which readily grows after exposure to the metal ions.

Synthesis of hydroxyapatite crystals using amino acid-capped gold nanoparticles as a scaffold.

Inorganic composites are of special interest for biomedical applications such as in dental and bone implants wherein the ability to modulate the morphology and size of the inorganic crystals is important. One interesting possibility to control the size of inorganic crystals is to grow them on nanoparticles. We report here the use of surface-modified gold nanoparticles as templates for the growth of hydroxyapatite crystals. Crystal growth is promoted by a monolayer of aspartic acid bound to the surface of the gold nanoparticles; the carboxylate ions in aspartic acid are excellent binging sites for Ca(2+) ions. Isothermal titration calorimetry studies of Ca(2+) ion binding with aspartic acid-capped gold nanoparticles indicates that the process is entropically driven and that screening of the negative charge by the metal ions leads to their aggregation. The aggregates of gold nanoparticles are believed to be responsible for assembly of the platelike hydroxyapatite crystals into quasi-spherical superstructures. Control experiments using uncapped gold nanoparticles and pure aspartic acid indicate that the amino acid bound to the nanogold surface plays a key role in inducing and directing hydroxyapatite crystal growth.

Using the dynamic, expanding liquid-liquid interface in a Hele-Shaw cell in crystal growth and nanoparticle assembly.

The liquid-liquid interface has been used with considerable success in the synthesis of advanced materials ranging from (bio)minerals to inorganic membranes to nanoparticles. In almost all such cases, the interface is static. The Hele-Shaw cell in which a viscous fluid is displaced by a less viscous one in a constrained manner has been invaluable in the study of dynamic instabilities at interfaces and in the study of viscous fingering pattern formation. However, the potential of the Hele-Shaw cell in carrying out reactions at the interface between the two fluids leading to the formation of inorganic materials has been largely unrecognized and underexploited. Realizing that the dynamic liquid-liquid interface in a Hele-Shaw cell would provide opportunities to control a variety of time-scales associated with material formation, we have started a program on the use of the Hele-Shaw cell in materials synthesis. In this discussion paper, we present some of our recent results on the growth of calcium carbonate crystals in the Hele-Shaw cell by the reaction of Ca2+ ions electrostatically complexed with carboxylate ions pinned to the interface with carbonate ions present in the aqueous part of the biphasic reaction medium. We show that both polymorph selectivity and the morphology of the crystals may be modulated by varying the experimental conditions in the cell. We also discuss the possibility of using the dynamic interface in the Hele-Shaw cell to cross-link gold nanoparticles in water through bifunctional linkers present in the oil phase and investigate the nature of the structures formed.

Biological synthesis of strontium carbonate crystals using the fungus Fusarium oxysporum.

The total biological synthesis of SrCO3 crystals of needlelike morphology arranged into higher order quasi-linear superstructures by challenging microorganisms such as fungi with aqueous Sr2+ ions is described. We term this procedure "total biological synthesis" since the source of carbonate ions that react with aqueous Sr2+ ions is the fungus itself. We believe that secretion of proteins during growth of the fungus Fusarium oxysporum is responsible for modulating the morphology of strontianite crystals and directing their hierarchical assembly into higher order superstructures.

Biosynthesis of CaCO3 crystals of complex morphology using a fungus and an actinomycete.

The biosynthesis of CaCO3 by reaction of aqueous Ca2+ ions with a fungus, Fusarium sp., and an actinomycete, Rhodococcus sp. (both plant organisms), is described. In the case of the fungus, cruciform-shaped calcite crystals are obtained (SEM picture A) while the actinomycete yielded the unstable polymorph of CaCO3, vaterite (SEM picture B). Specific proteins secreted by the microorganisms are responsible for the morphology and crystallography control observed. A highlight of this approach is that the microorganisms also provide CO2 for reaction with the Ca2+ ions, making the crystals completely biogenic.