Surfactant Semiconductors as Trojan Horses in Cell-Membranes for On-Demand and Spatial Regulation of Oxidative Stress.

Oxidative stress is a cause for numerous diseases and aging processes. Thus, researchers are keen to tune the level of intracellular stress and to learn from that. An unusual approach is presented here. The methodology involves multifunctional surfactants. Although their molecular design is nonbiological-a fullerenol head group attached covalently to pi-conjugated dyes-the surfactants possess superior biocompatibility. Using an intrinsic fluorescence signal as a probe, it is shown that the amphiphiles become incorporated into the Caco-2 cells. There, they are able to exhibit additional functions. The compound reduces cellular stress in dark reaction pathways. The antagonistic property is activated under irradiation, the photocatalytic production of reactive oxygen species (ROS), resulting in cell damage. The feature is activated even by near-infrared light (NIR-light) via a two-photon process. The properties as molecular semiconductors lead to a trojan horse situation and allows the programming of the spatial distribution of cytotoxicity.

The influence of structural gradients in large pore organosilica materials on the capabilities for hosting cellular communities.

Cells exist in the so-called extracellular matrix (ECM) in their native state, and numerous future applications require reliable and potent ECM-mimics. A perspective, which goes beyond ECM emulation, is the design of a host-material with features which are not accessible in the biological portfolio. Such a feature would, for instance, be the creation of a structural or chemical gradient, and to explore how this special property influences the biological processes. First, we wanted to test if macroporous organosilica materials with appropriate surface modification can act as a host for the implementation of human cells like HeLa or LUHMES. It was possible to use a commercially available polymeric foam as a scaffold and coat it with a thiophenol-containing organosilica layer, followed by biofunctionalization with biotin using click chemistry and the subsequent coupling of streptavidin-fibronectin to it. More importantly, deformation of the scaffold allowed the generation of a permanent structural gradient. In this work, we show that the structural gradient has a tremendous influence on the capability of the described material for the accommodation of living cells. The introduction of a bi-directional gradient enabled the establishment of a cellular community comprising different cell types in spatially distinct regions of the material. An interesting perspective is to study communication between cell types or to create cellular communities, which can never exist in a natural environment.

Molecular Semiconductor Surfactants with Fullerenol Heads and Colored Tails for Carbon Dioxide Photoconversion.

The leaf is a prime example of a material converting waste (CO2 ) into value with maximum sustainability. As the most important constituent, it contains the coupled photosystems II and I, which are imbedded in the cellular membrane of the chloroplasts. Can key functions of the leaf be packed into soap? We present next-generation surfactants that self-assemble into bilayer vesicles (similar to the cellular membrane), are able to absorb photons of two different visible wavelengths, and exchange excited charge carriers (similar to the photosystems), followed by conversion of CO2 (in analogy to the leaf). The amphiphiles contain five dye molecules as the hydrophobic entity attached exclusively to one hemisphere of a polyhydroxylated fullerene (Janus-type). We herein report on their surfactant, optical, electronic, and catalytic properties. Photons absorbed by the dyes are transferred to the fullerenol head, where they can react with different species such as CO2 to give formic acid.

Easy, efficient and versatile one-pot synthesis of Janus-type-substituted fullerenols.

An efficient one-pot synthesis for Janus-type fullerenol derivatives and how to characterize them is reported. This synthesis provides access to asymmetrically substituted fullerenol with five substituents on one pole of the fullerene and polyhydroxylation moieties, mostly ether and hydroxy groups, on the rest of the fullerene core. As substituents a broad variety of primary amines can be used to obtain Janus-type amphiphilic fullerenols in good to excellent yield. These fullerenol amphiphiles can serve as suitable precursors for further reactions resulting in new applications for fullerenols.

Organometallic, Nonclassical Surfactant with Gemini Design Comprising π-Conjugated Constituents Ready for Modification.

Surfactants are functional molecules comprising a water-compatible head group and a hydrophobic tail. One of their features is the formation of self-assembled structures in contact with water, for instance, micelles, vesicles, or lyotropic liquid crystals. One way to increase the functionality of surfactants is to implement moieties containing transition-metal species. Ferrocene-based surfactants represent an excellent example because of the distinguished redox features. In most existing ferrocene-based amphiphiles, an alkyl chain is classically used as the hydrophobic tail. We report the synthesis and properties of 1-triisopropylsilylethynyl-1'-trimethylammoniummethylferrocene (FcNMe3TIPS). In FcNMe3TIPS, ferrocene is part of the head group (Gemini design) but is also attached to a (protected) π-conjugated ethynyl group. Although this architecture differs from that of classical amphiphiles and those of other ferrocene-based amphiphiles, the compound shows marked surfactant properties comparable to those of lipids, exhibiting a very low value of critical aggregation concentration in water (cac = 0.03 mM). It forms classical micelles only in a very narrow concentration range, which then convert into monolayer vesicles. Unlike classical surfactants, aggregates already form at a very low concentration, far beneath that required for the formation of a monolayer at the air-water interface. At even higher concentration, FcNMe3TIPS forms lyotropic liquid crystals, not only in contact with water, but also in a variety of organic solvents. As an additional intriguing feature, FcNMe3TIPS is amenable to a range of further modification reactions. The TIPS group is easily cleaved, and the resulting ethynyl function can be used to construct heterobimetallic platinum-ferrocene conjugates with trans-Pt(PEt3)2X (X = Cl, I) complex entities, leading to a heterobimetallic surfactant. We also found that the benzylic α-position of FcNMe3TIPS is rather reactive and that the attached ammonium group can be exchanged by other substituents (e.g., -CN), which offers additional opportunities for further functionalization. Although FcNMe3TIPS is reversibly oxidized in voltammetric and UV-vis spectroelectrochemical experiments, the high reactivity at the α-position is also responsible for the instability of the corresponding ferrocenium ion, leading to a polymerization reaction.

Sweet surfactants: packing parameter-invariant amphiphiles as emulsifiers and capping agents for morphology control of inorganic particles.

Surfactants are not only pivotal constituents in any biological organism in the form of phospholipids, they are also essential for numerous applications benefiting from a large, internal surface, such as in detergents, for emulsification purposes, phase transfer catalysis or even nanoparticle stabilization. A particularly interesting, green class of surfactants contains glycoside head groups. Considering the variability of glycosides, a large number of surfactant isomers become accessible. According to established models in surfactant science such as the packing parameter or the hydrophilic lipophilic balance (HLB), they do not differ from each other and should, thus, have similar properties. Here, we present the preparation of a systematic set of glycoside surfactants and in particular isomers. We investigate to which extent they differ in several key features such as critical aggregation concentration, thermodynamic parameters, etc. Analytical methods like isothermal titration calorimetry (ITC), tensiometry, dynamic light scattering (DLS), small angle-X-ray scattering (SAXS), transmission electron microscopy (TEM) and others were applied. It was found that glycosurfactant isomers vary in their emulsification properties by up to two orders of magnitude. Finally, we have investigated the role of the surfactants in a microemulsion-based technique for the generation of zinc oxide (ZnO) nanoparticles. We found that the choice of the carbohydrate head has a marked effect on the shape of the formed inorganic nanocrystals.

Increasing the Resistance of Living Cells against Oxidative Stress by Nonnatural Surfactants as Membrane Guards.

The importation of construction principles or even constituents from biology into materials science is a prevailing concept. Vice versa, the cellular level modification of living systems with nonnatural components is much more difficult to achieve. It has been done for analytical purposes, for example, imaging, to learn something about intracellular processes. Cases describing the improvement of a biological function by the integration of a nonnatural (nano)constituent are extremely rare. Because biological membranes contain some kind of a surfactant, for example, phospholipids, our idea is to modify cells with a newly synthesized surfactant. However, this surfactant is intended to possess an additional functionality, which is the reduction of oxidative stress. We report the synthesis of a surfactant with Janus-type head group architecture, a fullerene C60 modified by five alkyl chains on one side and an average of 20 oxygen species on the other hemisphere. It is demonstrated that the amphiphilic properties of the fullerenol surfactant are similar to that of lipids. Not only quenching of reactive oxygen species (superoxide, hydroxyl radicals, peroxynitrite, and hydrogen peroxide) was successful, but also the fullerenol surfactant exceeds benchmark antioxidant agents such as quercetin. The surfactant was then brought into contact with different cell types, and the viability even of delicate cells such as human liver cells (HepG2) and human dopaminergic neurons (LUHMES) has proven to be extraordinarily high. We could show further that the cells take up the fullerenol surfactant, and as a consequence, they are protected much better against oxidative stress.

Added-Value Surfactants.

Surfactants are ubiquitous in cellular membranes, detergents or as emulsification agents. Due to their amphiphilic properties, they cannot only mediate between two domains of very different solvent compatibility like water and organic but also show fascinating self-assembly features resulting in micelles, vesicles, or lyotropic liquid crystals. The current review article highlights some approaches towards the next generation surfactants, for example, those with catalytically active heads. Furthermore, it is shown that amphiphilic properties can be obtained beyond the classical hydrophobic-hydrophilic interplay, for instance with surfactants containing one molecular block with a special shape. Whereas, classical surfactants are static, researchers have become more interested in species that are able to change their properties depending on external triggers. The article discusses examples for surfactants sensitive to chemical (e.g., pH value) or physical triggers (temperature, electric and magnetic fields).