Spherical silica nanoparticles of various particle sizes (B10 to 100 nm), produced by a modified Stoeber method employing amino acids as catalysts, are investigated using Dynamic Nuclear Polarization (DNP) enhanced Nuclear Magnetic Resonance (NMR) spectroscopy. This study includes ultra-sensitive detection of surface-bound amino acids and their supramolecular organization in trace amounts, exploiting the increase in NMR sensitivity of up to three orders of magnitude via DNP. Moreover, the nature of the silicon nuclei on the surface and the bulk silicon nuclei in the core (sub-surface) is characterized at atomic resolution. Thereby, we obtain unique insights into the surface chemistry of these nanoparticles, which might result in improving their rational design as required for promising applications, e.g. as catalysts or imaging contrast agents. The non-covalent binding of amino acids to surfaces was determined which shows that the amino acids not just function as catalysts but become incorporated into the nanoparticles during the formation process. As a result only three distinct Q-types of silica signals were observed from surface and core regions. We observed dramatic changes of DNP enhancements as a function of particle size, and very small particles (which suit in vivo applications better) were hyperpolarized with the best efficiency. Nearly one order of magnitude larger DNP enhancement was observed for nanoparticles with 13 nm size compared to particles with 100 nm size.We determined an approximate DNP penetration-depth (B4.2 or B5.7 nm) for the polarization transfer from electrons to the nuclei of the spherical nanoparticles. Faster DNP polarization buildup was observed for larger nanoparticles. Efficient hyperpolarization of such nanoparticles, as achieved in this work, can be utilized in applications such as magnetic resonance imaging (MRI). A IntroductionDNP increases the sensitivity of NMR experiments (signal-to-noise ratio, S/N), 1-3 enabling the study of low concentrated systems which were not in the scope of NMR until now. NMR signal enhancement is achieved by transferring large electron polarization to surrounding nuclei via DNP. In the last decade, there has been remarkable progress in solution and solid-state DNP-NMR as well as in imaging through the application of hyperpolarization methods. [4][5][6][7] As pointed out recently, this ''renaissance of DNP'' combined with high magnetic fields will further grow in the coming years, enabling demanding applications with better resolution. 8,9 Materials and biological systems such as membrane or microcrystalline proteins, 10-13 fibrils, 14 ligands bound to receptors, 15 polymers, [16][17][18] surface-bound species, 19-23 and other low concentrated samples were studied beneficially using DNP-NMR. 13,[24][25][26] Cryogenic temperatures are required to slow down nuclear and electron relaxation and to allow an efficient polarization transfer in solid-state DNP NMR experiments. In contrast to biological systems, 15,27-29 most technically relevant materials ...

Procedures for producing silica nanoparticles suitable for further amino functionalization and subsequent decoration with silica beads were investigated in a comparative way. Several methods, one based on tetrapropylammonium hydroxide, the classical Stöber synthesis, and two with amino acids (either lysine or arginine) as catalysts were employed and followed by means of DLS, SAXS, and TEM. The amino acid methods proved to be by far the most satisfactory ones, yielding highly spherical and monodisperse nanoparticles with a tunable size range of 15-100 nm. The surface of the particles could be functionalized with propylamine, which enabled to obtain positive surface charge at low pH and to tune the zeta potential by the pH in the range of +/- 40 mV. Finally, the modified particles were used to reduce silver (I) ions at high pH, leading to the formation of very small silver beads covering the silica surface and yielding a nanocomposite with a "raspberry" structure. Interestingly, this could be achieved without using any complementary reducing agent besides the particles themselves, thereby opening a very simple path to the formation of composite metal containing colloidal systems.

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The research topics of our group are in general from the field of physical chemistry of colloidal systems. Within this rather wide layout a large variety of quite different questions and systems are tackled, where the common bridging factor is the aim of understanding the properties of colloidal systems based on their mesoscopic structure and dynamics, which in turn are controlled by their molecular composition. With such an enhanced understanding of the correlation between mesoscopic structure and the macroscopic properties the goal then is to employ this knowledge in order to formulate increasingly complex colloidal system with correspondingly more variable and interesting functionalities. From this general context of investigations, some representative systems and questions that have been studied in recent time by us are covered in this text.They comprise the phase behaviour and the structures formed in solutions of surfactants and amphiphilic copolymers. Once these static properties are known, we also have a high interest in the dynamic properties and the kinetics of morphological transitions as they are observed under non-equilibrium conditions, since they are frequently encountered in applications. A key property of amphiphilic molecules is their ability to solubilise sparingly soluble compounds thereby forming microemulsions or nanoemulsions, where the ability to form such systems depends strongly on the molecular architecture of the amphiphiles. By turning to polymeric amphiphiles the concept of surfactants and their architecture can be extended largely towards more versatile structures, more complex self-assembly and much larger length and time scales. Another direction is the surfactant assisted formation of nanoparticles or mesoporous inorganic materials. By combining copolymers with other polymers, copolymers, colloids, or surfactants – for instance via electrostatically driven co-assembly – one may then form increasingly complex colloidal aggregates. By doing so one is able to control rheological properties or develop complex delivery systems, whose properties can be tailor-made by appropriate choice of the molecular build-up. This striving towards well controlled complexity achieved by means of self- and co-assembly then leads to increasingly more functional systems and is the key direction for future research activities in our group.

Composites of poly(glycidyl methacrylate) (PGMA) and L-lysine-coated silica nanoparticles with varying contents were prepared by in situ bulk polymerization using benzoyl peroxide (BPO) as free radical initiator. Silica nanoparticles covered by L-lysine molecules were synthesized using emulsion method. Dynamic light scattering measurements confirmed that the particles are highly monodisperse with the diameter of 10 nm and free of aggregates in the monomer (glycidyl methacrylate, GMA). Upon polymerization of the homogeneous particle/monomer dispersion, aggregates of individual silica nanoparticles are observed by tapping mode atomic force microscope (AFM). Amine and/or carboxylic acid sites on particle surface covalently react with the oxirane groups of the polymer backbone. The aggregation was substantially suppressed by using a difunctional comonomer divinyl benzene (DVB) in polymerization. A three-dimensional polymer network, P(GMA-DVB), forms throughout the system. This structure leads to significant progress in particle dispersion, therefore in physical properties of the resulting composite. We demonstrated that the composites prepared by crosslinked chains are thermally more stable and mechanically stiffer than those prepared by linear ones.