Michael Gradzielski

Systems chemistry: logic gates based on the stimuli-responsive gel–sol transition of a crown ether-functionalized bis(urea) gelator

A quite simple, achiral benzo-21-crown-7-substituted bis(urea) low-molecular weight gelator hierarchically assembles into helical fibrils, which further develop into bundles and finally form a stable gel in acetonitrile. The gel–sol transition can be controlled by three different molecular recognition events: K+ binding to the crown ethers, pseudorotaxane formation with secondary ammonium ions and Cl− binding to the urea units. Addition of a cryptand that scavenges the K+ ions and Ag+ addition to remove the chloride and bases/acids, which mediate pseudorotaxane formation, can reverse this process. With the gelator, and these chemical stimuli, a number of different systems can be designed that behave as logic gates. Depending on the choice of components, OR, AND, XOR, NOT, NOR, XNOR and INHIBIT gates have been realized. Thus, the gel–sol transition as a property of the system as a whole is influenced in a complex manner. For some cases, the type of logic gate is defined by input signal concentration so that an even more complex reaction of the gel towards the two input signals is achieved.

Evolution of ZnS Nanoparticles via Facile CTAB Aqueous Micellar Solution Route: A Study on Controlling Parameters

Synthesis of semiconductor nanoparticles with new photophysical properties is an area of special interest. Here, we report synthesis of ZnS nanoparticles in aqueous micellar solution of Cetyltrimethylammonium bromide (CTAB). The size of ZnS nanodispersions in aqueous micellar solution has been calculated using UV-vis spectroscopy, XRD, SAXS, and TEM measurements. The nanoparticles are found to be polydispersed in the size range 6–15 nm. Surface passivation by surfactant molecules has been studied using FTIR and fluorescence spectroscopy. The nanoparticles have been better stabilized using CTAB concentration above 1 mM. Furthermore, room temperature absorption and fluorescence emission of powdered ZnS nanoparticles after redispersion in water have also been investigated and compared with that in aqueous micellar solution. Time-dependent absorption behavior reveals that the formation of ZnS nanoparticles depends on CTAB concentration and was complete within 25 min.

Time dependence of nucleation and growth of silver nanoparticles generated by sugar reduction in micellar media

Synthesis of silver nanoparticles in homogeneous aqueous solutions of the precursors silver nitrate and three saccharides (two mono saccharides i.e. glucose and fructose and one disaccharide such as sucrose) has been performed. These Ag-nanoparticles can be derivatized by other surface treatments, as required. The anionic surfactant SDS was tested to investigate its effect on the dependence of size, growth rate, photoluminescence (PL) emission and polydispersity of the nanoparticles. The time evolution of UV-vis absorbance suggested that nucleation and growth rate markedly vary in a first order fashion w.r.t. Ag(+) salt concentration. The differences in the reducing ability of the saccharides were discussed with reference to their structure dependent adsorption behavior onto the particles. Changes in UV-vis, PL and FT-IR spectra during nucleation and growth of the nanoparticles were used to establish plausible mechanisms for the adsorption of surfactant on the particle surface, so as to restrict the growth. The results revealed a simple and easy strategy for synthesizing metal nanoparticles with well controlled shapes, sizes and structures.

Wrapping of nanoparticles by membranes

How nanoparticles interact with biomembranes is central for understanding their bioactivity. Biomembranes wrap around nanoparticles if the adhesive interaction between the nanoparticles and membranes is sufficiently strong to compensate for the cost of membrane bending. In this article, we review recent results from theory and simulations that provide new insights on the interplay of bending and adhesion energies during the wrapping of nanoparticles by membranes. These results indicate that the interplay of bending and adhesion during wrapping is strongly affected by the interaction range of the particle-membrane adhesion potential, by the shape of the nanoparticles, and by shape changes of membrane vesicles during wrapping. The interaction range of the particle-membrane adhesion potential is crucial both for the wrapping process of single nanoparticles and the cooperative wrapping of nanoparticles by membrane tubules.

Dynamics of Spontaneous Vesicle Formation in Fluorocarbon and Hydrocarbon Surfactant Mixtures

The spontaneous self-assembly of unilamellar vesicles was investigated by means of time-resolved synchrotron small-angle X-ray scattering. The self-assembly process was initiated by rapid mixing of anionic surfactant micelles with either zwitterionic or cationic surfactant micelles in equimolar ratio using a stopped-flow device. For the zwitteranionic systems, transient disklike mixed micelles are observed as structural intermediates prior to the onset of vesiculation. These disklike micelles display an exponential growth law, and above a critical size they close to form unilamellar vesicles. In the catanionic system, the earliest observable structures within the mixing time of 4 ms are unilamellar vesicles. Nevertheless, in both systems a narrow distribution of the vesicle size was observed at the initial stages of their formation. The subsequent evolution of the vesicle size distribution depends on the subtle differences in the bilayer composition and properties.

Supramolecular polymers as surface coatings: rapid fabrication of healable superhydrophobic and slippery surfaces.

Supramolecular polymerization for non-wetting surface coatings is described. The self-assembly of low-molecular-weight gelators (LMWGs) with perfluorinated side chains can be utilized to rapidly construct superhydrophobic, as well as liquid-infused slippery surfaces within minutes. The lubricated slippery surface exhibits impressive repellency to biological li-quids, such as human serum and blood, and very fast self-healing.

Growth, stability, optical and photoluminescent properties of aqueous colloidal ZnS nanoparticles in relation to surfactant molecular structure.

The interaction between organic molecules and the surface of nanoparticles (NPs) strongly affects the size, properties and applications of surface-modified metal sulfide semiconductor nanocrystals. From this viewpoint, we compared the influence of cationic surfactants with various chain lengths and anionic surfactants with different head groups, as surface modifiers during synthesis of ZnS NPs in aqueous medium. The surfactant adsorbs on the surface of the particles as micelle-like aggregates. These aggregates can form even at the concentration lower than critical micelle concentration (cmc) due to interaction between the polar groups and the NPs. The nature of interaction depends specifically on the surfactant polar group. The ability of surfactant to form the micelle-like aggregates on the surface of the NPs correlates with their cmc. This leads to the fact that the surfactant with longer tail stabilizes the NPs better since its cmc is lower. The adsorption of the surfactant on the NPs also stabilizes them by the change of their charge which is in accordance with the correlation of zeta potential with the particles stability. The energetics of surface states generating interesting photoluminescence (PL) properties in ZnS NPs has been governed by the nature of surfactant molecules. In general, the size, structure, and stability of the ZnS NPs can be controlled by the choice of suitable surfactant.

Versatile Phase Transfer of Gold Nanoparticles from Aqueous Media to Different Organic Media

A novel, simple, and very efficient method to prepare hydrophobically modified gold particles is presented. Gold nanoparticles of different sizes and polydispersities were prepared. The diameter of the gold particles ranges from 5 to 37 nm. All systems were prepared in aqueous solution stabilized by citrate and afterwards transferred into an organic phase by using amphiphilic alkylamine ligands with different alkyl chain lengths. The chain length was varied between 8 and 18 alkyl groups. Depending on the particle size and the alkylamine, different transfer efficiencies were obtained. In some cases, the phase transfer has a yield of about 100%. After drying, the particles can be redispersed in different organic solvents. Characterization of the particles before and after transfer was performed by using UV/Vis spectroscopy, transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS) techniques. The effect of organic solvents with various refractive indices on the plasmon band position was investigated.

Self-aggregation of mixtures of oppositely charged polyelectrolytes and surfactants studied by rheology, dynamic light scattering and small-angle neutron scattering.

In this study, the phase behavior, structure and properties of systems composed of the cationic, cellulose-based polycation JR 400 and the anionic surfactants sodium dodecylbenzenesulfonate (SDBS) or sodium dodecylethoxysulfate (SDES), mainly in the semidilute regime, were examined. This system shows the interesting feature of a very large viscosity increase by nearly 4 orders of magnitude as compared to the pure polymer solution already at very low concentrations of 1 wt%. By using rheology, dynamic light scattering (DLS), and small-angle neutron scattering (SANS), we are able to deduce systematic correlations between the molecular composition of the systems (characterized by the charge ratio Z=[+(polymer)]/[−(surfactant)]), their structural organization and the resulting macroscopic flow behavior. Mixtures in the semidilute regime with an excess of polycation charge form highly viscous network structures containing rodlike aggregates composed of surfactant and polyelectrolyte that are interconnected by the long JR 400 chains. Viscosity and storage modulus follow scaling laws as a function of surfactant concentration (η~c(s)(4); G(0)~c(s)(1.5)) and the very pronounced viscosity increase mainly arises from the strongly enhanced structural relaxation time of the systems. In contrast, mixtures with excess surfactant charges form solutions with viscosities even below those of the pure polymer solution. The combination of SANS, DLS, and rheology shows that the structural, dynamical, and rheological properties of these oppositely charged polyelectrolyte/surfactant systems can be controlled in a systematic fashion by appropriately choosing the systems composition.

Experimental Aspects of Colloidal Interactions in Mixed Systems of Liposome and Inorganic Nanoparticle and Their Applications

In the past few years, growing attention has been devoted to the study of the interactions taking place in mixed systems of phospholipid membranes (for instance in the form of vesicles) and hard nanoparticles (NPs). In this context liposomes (vesicles) may serve as versatile carriers or as a model system for biological membranes. Research on these systems has led to the observation of novel hybrid structures whose morphology strongly depends on the charge, composition and size of the interacting colloidal species as well as on the nature (pH, ionic strength) of their dispersing medium. A central role is played by the phase behaviour of phospholipid bilayers which have a tremendous influence on the liposome properties. Another central aspect is the incorporation of nanoparticles into vesicles, which is intimately linked to the conditions required for transporting a nanoparticle through a membrane. Herein, we review recent progress made on the investigations of the interactions in liposome/nanoparticle systems focusing on the particularly interesting structures that are formed in these hybrid systems as well as their potential applications.