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Helmut Cölfen

Publications and source records attributed to Helmut Cölfen.

31 records · Page 2Linked to original sources
PubMed2005

Nonclassical crystallization: mesocrystals and morphology change of CaCO3 crystals in the presence of a polyelectrolyte additive.

Crystallization of calcite from differently concentrated calcium chloride solutions by the CO2 gas diffusion technique in the presence of polystyrene sulfonate yields crystal superstructures with unusual morphology. From the typical calcite rhombohedra as a starting situation, the morphology can be systematically varied via rounded edges and truncated triangles to finally concavely bended lens-like superstructures. Although these "crystals" are apparently well-faceted in light microscopy, electron microscopy analysis and BET reveal that the structures are highly porous and are composed of almost perfectly 3D-aligned calcite nanocrystals scaffolded to the final, partly nicely curved superstructures. At high supersaturations, superstructures with changed symmetry indicative of dipolar interaction potentials between the building blocks are found. The present model case also gives evidence for the importance of nonclassical, mesoscopic processes in crystallization in general.

Journal Article↗
PubMed2004

Tectonic arrangement of BaCO3 nanocrystals into helices induced by a racemic block copolymer.

Morphosynthesis strategies inspired by biomineralization processes gives access to a wide range of fascinating and useful crystalline mesostructures. Biomimetic synthesis of inorganic materials with complex shapes can now be used to control the nucleation, tensorial growth, and alignment of inorganic crystals in a way previously not practicable. Double hydrophilic block copolymers (DHBCs) consisting of a hydrophilic block strongly interacting with inorganic minerals, and a non-interacting hydrophilic block, were recently introduced for the control of mineralization reactions. DHBCs are 'improved versions' of the previously used polyelectrolytes or amphiphiles and are extraordinarily effective in crystallization control. Here, we report on the formation of helices of achiral BaCO(3) nanocrystals in the presence of a racemic DHBC suggesting that a helical alignment can be induced by racemic polymers through selective adsorption on the (110) face of nanocrystals. This mechanism is the key for a better understanding of the self-assembly of chiral organic-inorganic superstructures that don't follow a direct template route.

Barium Compounds↗
PubMed2004

Solvent effect on mineral modification: selective synthesis of cerium compounds by a facile solution route.

A mild solution method has been designed for the selective synthesis of orthorhombic and hexagonal CeOHCO(3), as well as cubic CeO(2) crystals in an ethanol/water mixed solvent. This study added a new example for selectively controlling different cerium compounds by manipulating the balance between kinetics and thermodynamics in a mixed solvent system. The competitive reactions taking place in the ethanol/water system, phase transition, and shape evolution were fully investigated: they were found to be strongly dependent on the composition of the reaction media. The influence of the ethanol content in the mixed solvent and that of the reaction time on the phase transition and shape of orthorhombic and hexagonal CeOHCO(3) crystals is discussed in detail. Metastable hexagonal CeOHCO(3) can be trapped, even at 80 degrees C, in the ethanol/water solvent mixture without the need for the high temperature adopted by previous hydrothermal approaches. The evolution process of orthorhombic and metastable hexagonal phases under mild solution conditions is discussed for the first time. Supersaturation will become faster and more evident when water is replaced by ethanol, because the inorganic salts have a lower solubility in ethanol than in water, and this will generally favor the formation of the kinetic phase, such as the hexagonal CeOHCO(3) phase reported in this paper. The optical properties of the products with different phases and composition were investigated.

Journal Article↗
PubMed2004

On the role of block copolymer additives for calcium carbonate crystallization: small angle neutron scattering investigation by applying contrast variation.

The role of the double-hydrophilic block copolymer poly(ethylen glycol)-block-poly(methacrylic acid) (PEG-b-PMAA) on the morphogenesis of calcium carbonate (CaCO3) was studied by applying the contrast variation small angle neutron scattering technique. The morphology and size of CaCO3 crystals is strongly affected by the addition of PEG-b-PMAA. In order to determine the partial scattering functions of the polymer and CaCO3 mineral, we developed both an experimental and theoretical approach with a sophisticated method of their determination from the scattering intensity. Partial scattering functions give detailed information for each component. In particular, the partial scattering function of the polymer, Spp, shows a monotonic slope with Q(-2 to -3) where the scattering vector Q is low (Q < 0.01 Angstrom(-1)), which is a clear evidence that the polymer within the CaCO3 mineral has a mass fractal dimension. The other partial scattering functions reflected the geometry of the CaCO3 particles or the "interaction" of polymer and CaCO3 on a microscopic scale, which leads to a coherent view with Spp.

Journal Article↗
PubMed2004

Superstructures of temporarily stabilized nanocrystalline CaCO3 particles: morphological control via water surface tension variation.

In this paper, the formation of different complex morphologies of nanocrystalline CaCO3 under the control of double hydrophilic block copolymers (DHBCs) carrying phosphate groups is described. The DHBCs consist of a poly(ethylene glycol) (PEG) block and a pendant poly[2-(2-hydroxy ethyl)ethylene] block with different degrees of phosphorylation up to 40%, some of which show surface activity. The polymers furthermore temporarily stabilize CaCO3 nanocrystals, which are formed by slow CO2 evaporation from a supersaturated Ca(HCO3)2 solution (Kitano method). The polymers are active down to concentrations of 10(-4) g/L. In dependence of the nature and concentration of the DHBC, tunable complex shuttlecock flowerlike and other superstructures are formed, which are aggregates of CaCO3 vaterite nanoparticles with an enhanced stability of at least 2 months. It is shown that the aggregation starts around template CO2 gas bubbles at the air/water interface. The size and morphology of the growing aggregates depends on the polymer concentration, phosphorylation degree, and water surface tension. The latter determines when the aggregate sinks to the bottom, interrupting the further growth process. Variation of the water surface tension by addition of the nonionic surfactant Antharox CO880 also allows a variation of the aggregate morphology, thus implying the described method as simple and versatile for the generation of complex CaCO3 morphologies.

Journal Article↗
PubMed2004

Formation and optical properties of gold nanoparticles synthesized in the presence of double-hydrophilic block copolymers.

In this article, we present a systematic, controlled synthesis of water-dispersed, polymer-stabilized Au nanoparticles with different sizes by either self-reduction or ultraviolet (UV) irradiation-enhanced reduction in the presence of double hydrophilic block copolymers with different functional patterns. The morphology of the particles was found to be spherical, triangular, truncated triangular, and hexagonal under various conditions. In addition, both the particle size and shape could be controlled by variation of the functional group pattern of the block copolymers. With a hexacyclen functional block, we achieved a perfect match to the Au (111) face, resulting in extremely thin free-standing triangular and hexagonal nanoplatelets that show interference patterns in the electron beam due to deformations in the sub-Angstrom range. UV-visible spectra show that the plasmon absorption band can be fine tuned, depending on the type of the polymer and the irradiation power. The influence of the functional polymer groups and the irradiation on the formation of gold nanoparticles was investigated in more detail.

Colloids↗
PubMed2003

Hybrid colloid analysis combining analytical ultracentrifugation and flow-field flow fractionation.

Ferritin, the iron storage protein, is an organic-inorganic hybrid colloid consisting of a hollow protein capsule, which is filled with ferrihydride with up to 4500 iron atoms. Owing to the varying iron content and the resulting density differences, as well as the protein oligomerization, a particle size distribution is superimposed with a density distribution, making a precise analysis of ferritin by analytical ultracentrifugation difficult. This study describes how the information of the sedimentation coefficient distribution can be combined with the diffusion coefficient distribution obtained from flow-field flow fractionation to yield the buoyant molar mass of the oligomers in the mixture, extending the information content of each individual analytical method. In addition, the sedimentation and diffusion coefficients are compatible with a simple hard-sphere aggregation model, suggesting that the ferritin oligomers up to the pentamer have a globular solution structure.

Algorithms↗
PubMed2003

Higher-order organization by mesoscale self-assembly and transformation of hybrid nanostructures.

The organization of nanostructures across extended length scales is a key challenge in the design of integrated materials with advanced functions. Current approaches tend to be based on physical methods, such as patterning, rather than the spontaneous chemical assembly and transformation of building blocks across multiple length scales. It should be possible to develop a chemistry of organized matter based on emergent processes in which time- and scale-dependent coupling of interactive components generate higher-order architectures with embedded structure. Herein we highlight how the interplay between aggregation and crystallization can give rise to mesoscale self-assembly and cooperative transformation and reorganization of hybrid inorganic-organic building blocks to produce single-crystal mosaics, nanoparticle arrays, and emergent nanostructures with complex form and hierarchy. We propose that similar mesoscale processes are also relevant to models of matrix-mediated nucleation in biomineralization.

Journal Article↗
PubMed2002

Control of the morphogenesis of barium chromate by using double-hydrophilic block copolymers (DHBCs) as crystal growth modifiers.

A systematic morphosynthesis of barium chromate particles has been performed by using double-hydrophilic block copolymers (DHBCs), which consist of a hydrophilic solvating block and a hydrophilic binding block, as crystal growth modifiers to direct the controlled precipitation of barium chromate from aqueous solution. Several kinds of DHBCs with different functional groups -COOH, -PO3H2, -SO3H, -SH as well as PEG-poly(aminoamine) block-dendrimer copolymers were explored for crystallization and morphology control of barium chromate. Well-defined morphologies of BaCrO4 particles can be produced, such as more or less dendritic X-shaped, elongated X-shaped, or rodlike particles, flower-like plates, ellipsoids, spheres, nanofiber bundles, nanofibers, and other more complex morphologies. In the presence of the phosphonated copolymer PEG-b-PMAA-PO3H2 (degree of phosphonation: 21%) at pH 5, large conelike bundles of nanofibers ranging from 10 to 20 nm in diameter with lengths up to 150 microns can be produced at room temperature, whereas replacement of the covalently bound phosphonate groups by the ionic salt analogue dopant fails to produce this structure, indicating the importance of the functional polymer block structures. The time-resolved formation process of the bundles of nanofibres was investigated, showing a remarkable self-similarity. At temperatures higher than 50 degrees C, in plastic flasks or when undergoing continuous stirring, only ellipsoids or nearly spherical particles can be obtained. This shows that the fiber formation relies on heterogeneous nucleation and is in agreement with a recently published mechanism where fiber formation is due to the vectorially directed self-assembly of primary particles. Our results demonstrate that the integration of DHBCs, taking advantage of the experimental conditions such as crystallization sites, temperature, pH, and reactant concentration, will extend the possibilities for controlling the shape, size, and microstructures of the inorganic crystals by means of a simple mineralization process.

Journal Article↗
PubMed2002

The separation of racemic crystals into enantiomers by chiral block copolymers.

A series of chiral double hydrophilic block copolymers (DHBCs) was synthesized and employed as additives in the crystallization of calcium tartrate tetrahydrate (CaT). We found that appropriate polymers can slow down the formation of the thermodynamically most stable racemic crystals as well as the formation of one of the pure enantiomeric crystals so that chiral separation by crystallization occurs even when racemic crystals can be formed. In addition, the presence of DHBCs results in major modifications of crystal morphology, creating unusual morphologies of higher complexity. Our study demonstrates the potential application of chiral DHBCs in the control of chirality throughout crystallization, in particular for racemic crystal systems, and also shows that enantiomeric excess of one enantiomer can be maximized by the kinetic control of crystallization.

Amino Acids↗