Background-One of the features of high-risk atherosclerotic plaques is a preponderance of macrophages. Experimental studies with hyperlipidemic rabbits have shown that ultrasmall superparamagnetic particles of iron oxide (USPIOs) accumulate in plaques with a high macrophage content and that this induces magnetic resonance (MR) signal changes. The purpose of our study was to investigate whether USPIO-enhanced MRI can also be used for in vivo detection of macrophages in human plaques. Methods and Results-MRI was performed on 11 symptomatic patients scheduled for carotid endarterectomy before and 24 (nϭ11) and 72 (nϭ5) hours after administration of USPIOs (Sinerem) at a dose of 2.6 mg Fe/kg. Histological and electron microscopical analyses of the plaques showed USPIOs primarily in macrophages within the plaques in 10 of 11 patients. Histological analysis showed USPIOs in 27 of 36 (75%) of the ruptured and rupture-prone lesions and 1 of 14 (7%) of the stable lesions. Of the patients with USPIO uptake, signal changes in the post-USPIO MRI were observed by 2 observers in the vessel wall in 67 of 123 (54%) and 19 of 55 (35%) quadrants of the T2*-weighted MR images acquired after 24 and 72 hours, respectively. For those quadrants with changes, there was a significant signal decrease of 24% (95% CI, 33% to 15%) in regions of interest in the images acquired after 24 hours, whereas no significant signal change was found after 72 hours. Conclusions-Accumulation

A key issue in research on ferrofluids (dispersions of magnetic colloids) is the effect of dipolar interactions on their structure and phase behaviour, which is not only important for practical applications but gives fundamental insight in dipolar fluids in general. In 1970, de Gennes and Pincus predicted a Van der Waals-like phase diagram and the presence of linear chains of particles in ferrofluids in zero magnetic field. Despite many experimental studies, no direct evidence of the existence of linear chains of dipoles has been reported in the absence of magnetic field, although simulations clearly show the presence of chain-like structures. Here, we show in situ linear dipolar structures in ferrofluids in zero field, visualized on the particle level by electron cryo-microscopy on thin, vitrified films of organic dispersions of monodisperse metallic iron particles. On systematically increasing the particle size, we find an abrupt transition from separate particles to randomly oriented linear aggregates and branched chains or networks. When vitrified in a permanent magnetic field, these chains align and form thick elongated structures, indicating lateral attraction between parallel dipole chains. These findings show that the experimental model used is well suited to study the structural properties of dipolar particle systems.

The investigation of solution‐borne nanostructures by transmission electron microscopy (TEM) is a frequently used analytical method in materials chemistry. In many cases, the preparation of the TEM sample involves drying and staining steps, and the collection of images leads to the interaction of the specimen with the electron beam. Both aspects call for cautious interpretation of the resulting electron micrographs. Alternatively, a near‐native solvated state can be preserved by cryogenic vitrification and subsequent imaging by low‐dose cryogenic TEM. In this Minireview, we provide a critical analysis of sample preparation, and more importantly, of the acquisition and interpretation of electron micrographs. This overview should provide a framework for the application of (cryo)‐TEM as a powerful and reliable tool for the analysis of colloidal and self‐assembled structures with nanoscopic dimensions.

Controlled modification of horseradish peroxidase with an apolar polymer chain (see figure) by cofactor reconstitution leads to giant amphiphiles, which form vesicular aggregates in aqueous solution.

Inspired by the remarkable shapes and properties of CaCO(3) biominerals, many studies have investigated biomimetic routes aiming at synthetic equivalents with similar morphological and structural complexity. Control over the morphology of CaCO(3) crystals has been demonstrated, among other methods, by the use of additives that selectively allow the development of specific crystal faces, while inhibiting others. Both for biogenic and biomimetic CaCO(3), the crystalline state is often preceded by an amorphous precursor phase, but still limited information is available on the details of the amorphous-to-crystalline transition. By using a combination of cryoTEM techniques (bright field imaging, cryo-tomography, low dose electron diffraction and cryo-darkfield imaging), we show for the first time the details of this transition during the formation of hexagonal vaterite crystals grown in the presence of NH(4)(+) ions. The formation of hexagonal plate-like vaterite occurs via an amorphous precursor phase. This amorphous phase converts into the crystalline state through a solid state transformation in which order and morphology develop simultaneously. The mineral initially develops as polycrystalline vaterite which transforms into a single crystal directed by an NH(4)(+)-induced crystal plane that acts as a templating surface.

Calcium carbonate biomineralization uses complex assemblies of macromolecules that control the nucleation, growth, and positioning of the mineral with great detail. To investigate the mechanisms involved in these processes, for many years Langmuir monolayers have been used as model systems. Here, we descibe the use of cryogenic transmission electron microscopy in combination with selected area electron diffraction as a quasi-time-resolved technique to study the very early stages of this process. In this way, we assess the evolution of morphology, polymorphic type, and crystallographic orientation of the calcium carbonate formed. For this, we used a self-assembled Langmuir monolayer of a valine-based bisureido surfactant (1) spread on a CaCl2-containing subphase and deposited on a holey carbon TEM grid. In a controlled environment, the grid is exposed to an atmosphere containing NH3 and CO2 (the (NH4)2CO3 diffusion method) for precisely determined periods of time (reaction times 30-1800 s) before it was plunged into melting ethane. This procedure allows us to observe amorphous calcium carbonate (ACC) particles growing from a few tens of nanometers to hundreds of nanometers and then crystallizing to form [00.1] oriented vaterite. The vaterite in turn transforms to yield [10.0] oriented calcite. We also performed the reaction in the absence of monolayer or in the presence of a nondirective monolayer of surfactant containing an oligo(ethylene oxide) 2 head group. Both experiments also showed the formation of a transient amorphous phase followed by a direct conversion into randomly oriented calcite crystals. These results imply the specific though temporary stabilization of the (00.1) vaterite by the monolayer. However, experiments performed at higher CaCl2 concentrations show the direct conversion of ACC into [10.0] oriented calcite. Moreover, prolonged exposure to the electron beam shows that this transformation can take place as a topotactic process. The formation of the (100) calcite as final product under different conditions shows that the surfactant is very effective in directing the formation of this crystal plane. In addition, we present evidence that more than one type of ACC is involved in the processes described.

determined to be 50 and 2000 , respectively, using a calibrated oscillating quartz crystal thickness monitor. After deposition, the devices were encapsulated with epoxy (Loctite quick-set epoxy) under an argon atmosphere in order to minimize exposure to oxygen and moisture. All device measurements were made at room temperature.Photoluminescence and electroluminescence spectra were measured on a SPEX Fluorolog-2 equipped with a liquid N 2 cooled InGaAs detector (800± 1600 nm), or on a spectrometer consisting of an ISA-SPEX Triax 180 spectrograph equipped with a liquid N 2 cooled CCD detector (Hamamatsu CCD, 1024 64 pixel, 400±1100 nm). Emission quantum yields were measured by relative actinometry with H 2 TPP (u = 0.11) or ZnTPP (u = 0.033). Near-IR quantum yields were determined for Yb(TPP)L(OEt) on the CCD fluorescence system using the visible H 2 TPP and ZnTPP actinometers. Then the emission quantum yields for the Nd and Er complexes were determined relative to the Yb(TPP)L(OEt) using the SPEX Fluorolog-2 with the InGaAs detector.Power for electroluminescence (EL) measurements was supplied using a Keithley 228 voltage/current source. A 100 W primary standard quartz halogen lamp was used to calibrate the Triax 180 spectrograph/CCD detector system in irradiance units (lW cm 2 nm ±1 ). Measurements were made normal to the surface of the devices, and in the computation of the EL quantum efficiencies it was assumed that the spatial distribution of the emission was Lambertian [23]. External device quantum efficiencies were calculated as described in the literature [27].

Hydrogen bonding between urea groups of amphiphilic tri-block copolymers considerably affects their self-assembly in water, which results in a strong modification of morphology and viscosity of aqueous solutions; the hydrogen bonding motif in these amphiphilic copolymers allows molecular recognition of small molecules with complementary hydrogen bonding units.