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The role of transition metals in chemical reactions is often derived from probing the metal 3d states. However, the relation between metal site geometry and 3d electronic states, arising from multielectronic effects, makes the spectral data interpretation and modeling of these optical excited states a challenge. Here we show, using the well-known case of red ruby, that unique insights into the density of transition metal 3d excited states can be gained with 2p3d resonant inelastic X-ray scattering (RIXS). We compare the experimental determination of the 3d excited states of Cr3+ impurities in Al2O3 with 190 meV resolution 2p3d RIXS to optical absorption spectroscopy and to simulations. Using the crystal field multiplet theory, we calculate jointly for the first time the Cr3+ multielectronic states, RIXS, and optical spectra based on a unique set of parameters. We demonstrate that (i) anisotropic 3d multielectronic interactions causes different scaling of Slater integrals, and (ii) a previously not observed doublet excited state exists around 3.35 eV. These results allow to discuss the influence of interferences in the RIXS intermediate state, of core–hole lifetime broadenings, and of selection rules on the RIXS intensities. Finally, our results demonstrate that using an intermediate excitation energy between L3 and L2 edges allows measurement of the density of 3d excited states as a fingerprint of the metal local structure. This opens up a new direction to pump-before-destroy investigations of transition metal complex structures and reaction mechanisms.

The Co 2p

Silica is a promising carrier material for nanoparticle-facilitated drug delivery, gene therapy, and molecular imaging. Understanding of their pharmacokinetics is important to resolve bioapplicability issues. Here we report an extensive study on bare and lipid-coated silica nanoparticles in mice. Results obtained by use of a wide variety of techniques (fluorescence imaging, inductively coupled plasma mass spectrometry, magnetic resonance imaging, confocal laser scanning microscopy, and transmission electron microscopy) showed that the lipid coating, which enables straightforward functionalization and introduction of multiple properties, increases bioapplicability and improves pharmacokinetics.

In this work, we show strong experimental evidence in favor of a proposed incorporation mechanism of hydrophobic semiconductor nanocrystals (or quantum dots, QDs) in monodisperse silica spheres (diameter ∼35 nm) by a water-in-oil (W/O) reverse microemulsion synthesis. Fluorescence spectroscopy is used to investigate the rapid ligand exchange that takes place at the QD surface upon addition of the various synthesis reactants. It is found that hydrolyzed TEOS has a high affinity for the QD surface and replaces the hydrophobic amine ligands, which enables the transfer of the QDs to the hydrophilic interior of the micelles where silica growth takes place. By hindering the ligand exchange using stronger binding thiol ligands, the position of the incorporated QDs can be controlled from centered to off-center and eventually to the surface of the silica spheres. The proposed incorporation mechanism explains how we can have high control over the incorporation of single QDs exactly in the middle of silica spheres. It is likely that the proposed mechanism also applies to the incorporation of other hydrophobic nanocrystals in silica using the same method. In conjunction with our findings, we were able to make QD/silica particles with an unprecedented quantum efficiency of 35%.

To fully characterize the Co-III-'nitrene radical' species that are proposed as intermediates in nitrene transfer reactions mediated by cobalt(II) porphyrins, different combinations of cobalt(II) complexes of porphyrins and nitrene transfer reagents were combined, and the generated species were studied using EPR, UV-vis, IR, VCD, UHR-ESI-MS, and XANES/XAFS measurements. Reactions of cobalt(II) porphyrins 1(P1) (P1 = meso-tetraphenylporphyrin (TPP)) and 1(P2) (P2 = 3,5-Di(t)Bu-ChenPhyrin) with organic azides 2(Ns) (NsN(3)), 2(Ts) (TsN3), and 2(Troc) (TrocN(3)) led to the formation of mono-nitrene species 3(Ns)(P1), 3(Ts)(P2), and 3(Troc)(P2), respectively, which are best described as [Co-III(por)(NR ''(center dot-))] nitrene radicals (imidyl radicals) resulting from single electron transfer from the cobalt(II) porphyrin to the 'nitrene' moiety (Ns: R '' = -SO2-p-C6H5NO2; Ts: R '' = -SO2C6H6; Troc: R '' = -C(O)OCH2CCl3). Remarkably, the reaction of 1(P1) with N-nosyl iminoiodane (PhI=NNs) 4(Ns) led to the formation of a bis-nitrene species 5(Ns)(P1). This species is best described as a triple-radical complex [(por ''(center dot-))Co-III(NR ''(center dot-))(2)] containing three ligand-centered unpaired electrons: two nitrene radicals (NR?(-)) and one oxidized porphyrin radical (por(center dot-)). Thus, the formation of the second nitrene radical involves another intramolecular one-electron transfer to the "nitrene" moiety, but now from the porphyrin ring instead of the metal center. Interestingly, this bis-nitrene species is observed only on reacting 4(Ns) with 1(P1). Reaction of the more bulky 1(P2) with 4(Ns) results again in formation of mainly mono-nitrene species 3(Ns)(P2) according to EPR and ESI-MS spectroscopic studies. The mono- and bis-nitrene species were initially expected to be five- and six-coordinate species, respectively, but XANES data revealed that both mono- and bis-nitrene species are six-coordinate Oh species. The nature of the sixth ligand bound to cobalt(III) in the mono-nitrene case remains elusive, but some plausible candidates are NH3, NH2-, NsNH(-), and OH-; NsNH(-) being the most plausible. Conversion of mono-nitrene species 3(Ns)(P1) into bis-nitrene species 5(Ns)(P1) upon reaction with 4(Ns) was demonstrated. Solutions containing 3(Ns)(P1) and 5(Ns)(P1) proved to be still active in catalytic aziridination of styrene, consistent with their proposed key involvement in nitrene transfer reactions mediated by cobalt(II) porphyrins.

The present status of in-situ scanning transmission X-ray microscopy (STXM) is reviewed, with an emphasis on the abilities of the STXM technique in comparison with electron microscopy. The experimental aspects and interpretation of X-ray absorption spectroscopy (XAS) are briefly introduced and the experimental boundary conditions that determine the potential applications for in-situ XAS and in-situ STXM studies are discussed. Nanoscale chemical imaging of catalysts under working conditions is outlined using cobalt and iron Fischer-Tropsch catalysts as showcases. In the discussion, we critically compare STXM-XAS and STEM-EELS (scanning transmission electron microscopy-electron energy loss spectroscopy) measurements and indicate some future directions of in-situ nanoscale imaging of catalytic solids and related nanomaterials.

Multimodal contrast agents based on highly luminescent quantum dots (QDs) combined with magnetic nanoparticles (MNPs) or ions form an exciting class of new materials for bioimaging. With two functionalities integrated in a single nanoparticle, a sensitive contrast agent for two very powerful and highly complementary imaging techniques [fluorescence imaging and magnetic resonance imaging (MRI)] is obtained. In this review, the state of the art in this rapidly developing field is given. This is done by describing the developments for four different approaches to integrate the fluorescence and magnetic properties in a single nanoparticle. The first type of particles is created by the growth of heterostructures in which a QD is either overgrown with a layer of a magnetic material or linked to a (superpara, or ferro) MNP. The second approach involves doping of paramagnetic ions into QDs. A third option is to use silica or polymer nanoparticles as a matrix for the incorporation of both QDs and MNPs. Finally, it is possible to introduce chelating molecules with paramagnetic ions (e.g., Gd-DTPA) into the coordination shell of the QDs. All different approaches have resulted in recent breakthroughs and the demonstration of the capability of bioimaging using both functionalities. In addition to giving an overview of the most exciting recent developments, the pros and cons of the four different classes of bimodal contrast agents are discussed, ending with an outlook on the future of this emerging new field.

An important challenge in medical diagnostics is to design all-in-one contrast agents that can be detected with multiple techniques such as magnetic resonance imaging (MRI), X-ray computed tomography (CT), positron emission tomography (PET), single photon emission tomography (SPECT) or fluorescence imaging (FI). Although many dual labeled agents have been proposed, mainly for combined MRI/FI, constructs for three imaging modalities are scarce. Here gold/silica nanoparticles with a poly(ethylene glycol), paramagnetic and fluorescent lipid coating were synthesized, characterized and applied as trimodal contrast agents to allow for nanoparticle-enhanced imaging of macrophage cells in vitro via MRI, CT and FI, and mice livers in vivo via MRI and CT. This agent can be a useful tool in a multitude of applications, including cell tracking and target-specific molecular imaging, and is a step in the direction of truly multi-modal imaging.

We study colloidal gels formed upon centrifugation of dilute suspensions of spherical colloids (radius 446 nm) that interact through a long-range electrostatic repulsion (Debye length approximately 850 nm) and a short-range depletion attraction (approximately 12.5 nm), by means of confocal scanning laser microscopy (CSLM). In these systems, at low colloid densities, colloidal clusters are stable. Upon increasing the density by centrifugation, at different stages of cluster formation, we show that colloidal gels are formed that significantly differ in structure. While significant single-particle displacements do not occur on the hour time scale, the different gels slowly evolve within several weeks to a similar structure that is at least stable for over a year. Furthermore, while reference systems without long-range repulsion collapse into dense glassy states, the repulsive colloidal gels are able to support external stress in the form of a centrifugal field of at least 9g.

Colloidal platelets of hydrotalcite, a layered double hydroxide, have been prepared by coprecipitation at pH 11-12 of magnesium nitrate and aluminum nitrate at two different magnesium to aluminum ratios. Changing the temperature and ionic strength during hydrothermal treatment, the platelets were tailored to different sizes and aspect ratios. Amino-modified polyisobutylene molecules were grafted onto the platelets following a convenient new route involving freeze-drying. Organic dispersions in toluene were prepared of the particles with the largest size and highest aspect ratio. The colloidal dispersions prepared in this way showed isotropic-nematic phase transitions above a limiting concentration in a matter of days. The number density at the transition and the width of the biphasic region were determined and compared to theory. The orientation of the platelets in nematic droplets (tactoids) and at the isotropic-nematic interface were analyzed by polarization microscopy. It was observed that sedimentation induces a nematic layer in samples that are below the limiting concentration for isotropic-nematic phase separation. No nematic phase was observed in the initial aqueous suspensions of the ungrafted particles.

High density lipoprotein (HDL) is an important natural nanoparticle that may be modified for biomedical imaging purposes. Here we developed a novel technique to create unique multimodality HDL mimicking nanoparticles by incorporation of gold, iron oxide, or quantum dot nanocrystals for computed tomography, magnetic resonance, and fluorescence imaging, respectively. By including additional labels in the corona of the particles, they were made multifunctional. The characteristics of these nanoparticles, as well as their in vitro and in vivo behavior, revealed that they closely mimic native HDL.

Silica particles as a nanoparticulate carrier material for contrast agents have received considerable attention the past few years, since the material holds great promise for biomedical applications. A key feature for successful application of this material in vivo is biocompatibility, which may be significantly improved by appropriate surface modification. In this study, we report a novel strategy to coat silica particles with a dense monolayer of paramagnetic and PEGylated lipids. The silica nanoparticles carry a quantum dot in their center and are made target-specific by the conjugation of multiple alphavbeta3-integrin-specific RGD-peptides. We demonstrate their specific uptake by endothelial cells in vitro using fluorescence microscopy, quantitative fluorescence imaging, and magnetic resonance imaging. The lipid-coated silica particles introduced here represent a new platform for nanoparticulate multimodality contrast agents.