Regina Klein

Stabilization of amorphous calcium carbonate in inorganic silica-rich environments.

In biomineralization, living organisms carefully control the crystallization of calcium carbonate to create functional materials and thereby often take advantage of polymorphism by stabilizing a specific phase that is most suitable for a given demand. In particular, the lifetime of usually transient amorphous calcium carbonate (ACC) seems to be thoroughly regulated by the organic matrix, so as to use it either as an intermediate storage depot or directly as a structural element in a permanently stable state. In the present study, we show that the temporal stability of ACC can be influenced in a deliberate manner also in much simpler purely abiotic systems. To illustrate this, we have monitored the progress of calcium carbonate precipitation at high pH from solutions containing different amounts of sodium silicate. It was found that growing ACC particles provoke spontaneous polymerization of silica in their vicinity, which is proposed to result from a local decrease of pH nearby the surface. This leads to the deposition of hydrated amorphous silica layers on the ACC grains, which arrest growth and alter the size of the particles. Depending on the silica concentration, these skins have different thicknesses and exhibit distinct degrees of porosity, therefore impeding to varying extents the dissolution of ACC and energetically favored transformation to calcite. Under the given conditions, crystallization of calcium carbonate was slowed down over tunable periods or completely prevented on time scales of years, even when ACC coexisted side by side with calcite in solution.

Choline carboxylate surfactants: biocompatible and highly soluble in water

With choline as a beneficial counterion of biological origin, long-chain carboxylates become water soluble at room temperature.

Alkali Metal Oligoether Carboxylates—A New Class of Ionic Liquids

On the way to greener ILs: The combination of a short oligoether carboxylate (CH3O-(CH2CH2O)3-CH2COO-) with small alkali metal cations leads to the formation of a new class of ionic liqs. that exhibit high thermal and electrochem. stability as well as low cytotoxicity.

Oligoether Carboxylates: Task-Specific Room-Temperature Ionic Liquids

Recently, a new family of ionic liquids based on oligoether carboxylates was introduced. 2,5,8,11-Tetraoxatridecan-13-oate (TOTO) was shown to form room-temperature ionic liquids (RTILs) even with small alkali ions such as lithium and sodium. However, the alkali TOTO salts suffer from their extremely high viscosities and relatively low conductivities. Therefore, we replaced the alkali cations by tetraalkylammonium (TAA) ions and studied the TOTO salts of tetraethyl- (TEA), tetrapropyl- (TPA), and tetrabutylammonium (TBA). In addition, the environmentally benign quaternary ammonium ion choline (Ch) was included in the series. All salts were found to be ionic liquids at ambient temperatures with a glass transition typically at around -60 °C. Viscosities, conductivities, solvent polarities, and Kamlet-Taft parameters were determined as a function of temperature. When using quaternary ammonium ions, the viscosities of the resulting TOTO ionic liquids are >600 times lower, whereas conductivities increase by a factor of up to 1000 compared with their alkali counterparts. Solvent polarities further reveal that choline and TAA cations yield TOTO ionic liquids that are more polar than those obtained with the, per se, highly polar sodium ion. Results are discussed in terms of ion-pairing and structure-breaking concepts with regard to a possible complexation ability of the TOTO anion.

Biodegradability and cytotoxicity of choline soaps on human cell lines: effects of chain length and the cation

Using choline as a counterion in fatty acid surfactants substantially increases their water solubility as compared to classical sodium and potassium soaps, and thereby enables the application of desirable longer-chain derivatives at ambient temperature. Since choline can be decomposed both physiologically and environmentally, corresponding fatty acid soaps are considered to be highly biocompatible. Recent toxicity and biodegradability studies of choline ionic liquids, including anions such as short- and middle-chain alkanoates, have verified the expected low toxic impact. However, according to the European Cosmetic Directive 76/768/EEC, all salts of choline are forbidden in cosmetic products, mainly just due to its classification as a quaternary ammonium ion. In order to facilitate their application in the future, we have investigated the biodegradability of choline soaps (ChCm) with alkyl chain lengths of m = 12–18 according to the OCDE 301F standard. Further, the cytotoxicity of ChCm surfactants with m = 8–16 was determined, both for odd- and even-numbered fatty acids. Studies were carried out using two different human cell lines, namely cervix carcinoma cells (HeLa) and keratinocytes (SK-Mel-28). For a better comparability to common soaps and to shed light on the influence of the cation, sodium and potassium homologues were also investigated. Results reveal an unexpected non-linear relationship between the hydrophobic chain length and the IC50 value. Most importantly, the presented data show that IC50 values of ChCm surfactants coincide with those of the widely applied sodium and potassium soaps. This demonstrates that choline carboxylate surfactants are harmless and thus strongly supports their applicability in customer end products.

Choline alkylsulfates - New promising green surfactants

In this work we show how a new promising green and highly water-soluble surfactant can be designed based on recent progress in the knowledge of counterion-headgroup binding and crystallization behavior. The result is the combination of a most classical surfactant anion, dodecylsulfate (DS), with choline (Ch), a natural green cation. The advantage of the physiological metabolite choline is its bulky structure that prevents ChDS from easy crystallization and thus leads to a considerable lowering of the Krafft point down to 0°C. The counterion-headgroup binding is reflected by the aqueous phase behavior of ChDS. Conductivity, surface tension, and cryo-TEM measurements allow the characterization of the dilute micellar region, while the penetration scan technique enables the establishment of a preliminary aqueous phase diagram. In addition, the influence of different mono- and divalent salts on the solubility of ChDS is investigated. The results are compared to the alkali sulfate and alkylcarboxylate homologs, and reveal that ChDS is less sensitive towards addition of salts than, for instance, choline carboxylates due to an increased counterion-headgroup association. Further, cytotoxicity tests on HeLa and SK-Mel 28 cells are presented and compared to other surfactants, showing that ChDS is no more harmful than its sodium counterpart SDS. Taken together, our findings highlight that the harmless green cation choline is of great potential for the design of new surfactants.

Thermotropic Phase Behavior of Choline Soaps

Choline carboxylates (ChCm with m = 12-18) are simple biocompatible anionic surfactants with very low Krafft temperatures, possessing a rich aqueous phase behavior. In the present work, we have investigated the thermotropic mesomorphism of anhydrous ChCm salts for m = 12-18. Transition temperatures and enthalpies determined by differential scanning calorimetry reveal that all investigated compounds exhibit three different phases between -20 and 95 °C. The phases were further characterized by optical polarizing microscopy, NMR spin-spin relaxation, and X-ray scattering measurements. The nature of the phases was identified with increasing temperature as crystalline, semicrystalline, and liquid-crystalline lamellar. Even long-chain choline carboxylates (m = 18) were found to melt into a lamellar liquid-crystalline phase below 100 °C. Accordingly, with choline as counterion in simple fatty acid soaps, not only the water solubility is considerably enhanced but also the melting points are substantially reduced, hence facilitating thermotropic mesomorphism at temperatures between 35 and 95 °C. Thus, simple choline soaps with m = 12-18 may be classified as ionic liquids.

Aqueous phase behaviour of choline carboxylate surfactants—exceptional variety and extent of cubic phases

Choline carboxylate surfactants are powerful alternatives to the well-known classical alkali soaps, since they exhibit substantially increased water solubility while maintaining biocompatibility, in contrast to simple quaternary ammonium ions. In the present study, we report the aqueous binary phase diagrams and a detailed investigation of the lyotropic liquid crystalline phases formed by choline carboxylate surfactants (ChCm) with chain lengths ranging from m = 12–18 and at surfactant concentrations of up to 95–98 wt%. The identification of the lyotropic mesophases and their sequence was achieved by the penetration scan technique. Structural details are elucidated by small-angle X-ray scattering (SAXS). The general sequence of mesophases with increasing soap concentration was found to be as follows: micellar (L1), discontinuous cubic (I1), hexagonal (H1), bicontinuous cubic (V1) and lamellar (Lα). The main difference to the phase behavior of alkali soaps or of other mono-anionic surfactants is the appearance and large extent of a discontinuous cubic phase with two or even more different symmetries. The obtained phase diagrams further highlight the extraordinarily high water solubility of ChCm soaps. Finally, structural parameters of ChCm salts such as the cross-sectional area at the polar–nonpolar interface are compared to those of alkali soaps and discussed in the terms of specific counterion binding and packing constraints.

Low Toxic Ionic Liquids, Liquid Catanionics, and Ionic Liquid Microemulsions

In the future the demand of sustainable and low toxic surfactants and solvents will constantly increase. In this article, we present some new approaches to meet these requirements. Whereas ionic liquids are often based on imidazolium ions, we will show that there are also much less toxic ones, especially with choline as cation. Choline salts, even if solid at room temperature, can advantageously be mixed with other sustainable solids to form deep eutectic solvents, that is, “green” liquids at room temperature. Further, choline can be used to dissolve long-chain carboxylates in water thus maybe permitting new applications of soaps. Alternatively, choline and other natural cations can be part of promising low toxic cationic surfactants. By combining them with ethoxylated carboxylates, interesting charged room temperature liquid surfactant combinations can be obtained. Finally, we shortly discuss the potential benefits of ionic liquids in microemulsions.

Precipitation and Crystallization Kinetics in Silica Gardens

Abstract Silica gardens are extraordinary plant‐like structures resulting from the complex interplay of relatively simple inorganic components. Recent work has highlighted that macroscopic self‐assembly is accompanied by the spontaneous formation of considerable chemical gradients, which induce a cascade of coupled dissolution, diffusion, and precipitation processes occurring over timescales as long as several days. In the present study, this dynamic behavior was investigated for silica gardens based on iron and cobalt chloride by means of two synchrotron‐based techniques, which allow the determination of concentration profiles and time‐resolved monitoring of diffraction patterns, thus giving direct insight into the progress of dissolution and crystallization phenomena in the system. On the basis of the collected data, a kinetic model is proposed to describe the relevant reactions on a fundamental physicochemical level. The results show that the choice of the metal cations (as well as their counterions) is crucial for the development of silica gardens in both the short and long term (i.e. during tube formation and upon subsequent slow equilibration), and provide important clues for understanding the properties of related structures in geochemical and industrial environments.