Search

Among the most reliable techniques for exfoliation of two-dimensional (2D) layered materials, sonication-assisted liquid-phase exfoliation (LPE) is considered as a cost-effective and straightforward method for preparing graphene and its 2D inorganic counterparts at reasonable sizes and acceptable levels of defects. Although there were rapid advances in this field, the effect and outcome of the sonication frequency are poorly understood and often ignored, resulting in a low exfoliation efficiency. Here, we demonstrate that simple mild bath sonication at a higher frequency and low power positively contributes to the thickness, size, and quality of the final exfoliated products. We show that monolayer graphene flakes can be directly exfoliated from graphite using ethanol as a solvent by increasing the frequency of the bath sonication from 37 to 80 kHz. The statistical analysis shows that ∼77% of the measured graphene flakes have a thickness below three layers with an average lateral size of 13 μm. We demonstrate that this approach works for digenite (Cu9S5) and silver sulfide (Ag2S), thus indicating that this exfoliation technique can be applied to other inorganic 2D materials to obtain high-quality few-layered flakes. This simple and effective method facilitates the formation of monolayer/few layers of graphene and transition metal chalcogenides for a wide range of applications.

Long-range structures and dynamics are central to coordination chemistry, yet are hard to identify experimentally. By combining polarized low-frequency Raman spectroscopy with single crystal XRD to study barium nitrilotriacetate, a metal-organic coordination polymer and a useful pyrolysis precursor, we could assign Raman peaks experimentally to layer shear motions and perpendicular hydrogen bond vibrations. These directional long-range interactions further determined the preferred fracture directions during crystallization, establishing an important link between structural motifs in the precursor, and the porosity of the carbon it yields upon pyrolysis.

The newly emerging demand for ‘beyond-lithium’ electrochemical energy storage systems necessitates the development of alternative options in providing sustainable cost-effective storage capabilities. In pursuit of discovering such a solution, the intercalation of bisulfate anions into graphite in 17 ​M ​H2SO4 solutions has been revaluated. Although the insertion process of bisulfate into graphite was extensively studied many years ago, only poor electrochemical performance has been demonstrated. In this work, we discovered the superior performance of the graphite bisulfate system, associated with the electrodes’ fabrication method which presents a high energy density of more than 80 ​mW ​h/g and a surprising rate capability (75 ​mW ​h/g was obtained at 15 ​C) alongside impressive long-term stability of more than 1500 cycles with only 5% capacity fading. Potentiostatic intermittent titration technique followed by slow-scan-rate cyclic voltammetry (SSCV) was used to shed light on the bisulfate intercalation process. Combining the bisulfate intercalation into the graphite with a highly reversible proton insertion process into Ti3C2 MXene in such a concentrated acidic environment allows the development of a dual-ion device composed of graphite positive electrode (cathode) and MXene negative electrode (anode). This asymmetric system shows a high energy density of 35 ​mW ​h/g, good cyclability and an extended potential window of 1.5 ​V, demonstrating new opportunities for further developments of intercalation electrodes for large energy storage.

Distinguishing between d and l enantiomers is of important scientific interest, especially for the pharmaceutical industry. Enantiomeric differentiation in the solid form is repeatedly presented as a challenge in the research community. Raman spectroscopy is a nondestructive tool, widely used for the characterization of different materials by probing their vibrational modes. The low-frequency region of the Raman spectrum reveals lattice-level interactions and global fluctuations in the molecule. Lower frequencies correspond to vibrations arising from weaker bonds and long-range interactions and hence are very susceptible to polarization changes. This work presents low-frequency Raman (LFR) spectroscopy as a facile technique to identify enantiomers. The optical setup of conventional Raman spectroscopy is engineered such that the excitation and collection geometries use an asymmetrical focal cone. In addition, a half-wave retarder is added to the excitation path and a Glan-Taylor polarizer is added to the collection path, and these modifications allow us to select the polarization plane for both excitation and collection geometries. The asymmetry in the foci when using a polarized beam for excitation provides different intensities of the collected signal for each polarization plane. In a calibrated system, one can define the chirality of an analyte by comparing the intensity of the LFR signal along orthogonal sets of polarization planes. For nonchiral molecules, the spectral intensity is always higher in the co-polarized plane when compared to the orthogonally depolarized plane, as expected. This contrast in the intensity of Raman spectra serves as a distinct tool for identifying enantiomers.

Transition-metal dichalcogenides (TMDCs) are unique layered materials with exotic properties. So, examining their structures holds tremendous importance. 2H-MoSe

Raman spectroscopy is a widely used characterization technique in material science. It is a non-destructive tool with relatively simple instrumentation, and provides intrinsic qualitative information of analytes by probing their vibrational modes. In many cases, Raman enhancement is essential for detecting low-intensity signals in high-noise environments, spectrally unresolved features, and hidden modes. Here we present optical and Raman spectroscopic characterization of fullerene C 60 in a gold microcavity. The fabrication of single-layered gold mirrors is facile, low cost and direct but was proven to give considerably significant enhancement. The findings of this work demonstrate the cavity resonance as a powerful tool in obtaining tunability over individual peak for selective enhancement in the tuned spectral range. The PL of the material within the cavity has demonstrated a red shift assumed to be caused by the low-energy transitions. These transitions are induced by virtual low-energy states generated by the cavity. We further observe that adopting this principle enables resolution of active Raman modes that until now were unobserved. Finally, we assigned the new experimentally observed modes to the corresponding motions calculated by DFT.

The pharmaceutical industry is in need of new techniques to identify the chirality of solids due to regulatory and safety concerns regarding the biological activity of enantiomers. In this study, we present for the first time the application of low-frequency Raman spectroscopy as a new and sensitive method for analyzing the chiral purity of crystals. Using this method, we were able to identify small amounts, as low as 1 % w/w, of an enantiomer in racemic crystals. To demonstrate the capabilities of the method, we used a model system based on chiral crystals of enantiopure, racemic crystals and their mixtures in various ratios. We found that the low-frequency Raman spectra of racemic and enantiopure crystals are significantly different, reflecting the different hydrogen bond networks. Moreover, a comparison of the sensitivity of enantiomeric excess in chiral crystals to that of circular dichroism and X-ray diffraction measurements showed that low-frequency Raman attains high sensitivity comparable to chiral optical methods used for solutions. Overall, our proposed approach of using Raman spectroscopy for determining enantiomeric excess in crystals is simple, fast, and offers a high degree of chiral sensitivity.

LiNi0.8Co0.1Mn0.1O2 (NCM811) is a promising cathode material for long range electric vehicles. However, the material suffers severe chemo-mechanical degradation that can cause gradual capacity loss upon prolonged cycling. Surface passivation of NMC811 was demonstrated to help in retaining the structural integrity of the material upon extended cycling. Herein, we report the surface passivation of the NCM811 using Li2S and Na2S precursors via direct and simple wet chemical treatment, for the mitigation of parasitic reactions at the electrode electrolyte interphase. This phenomenon is accompanied by increase in the oxidation state of sulfur (from sulfide to sulfate) and partial reduction in the oxidation state of nickel. Electrochemical performance measurements show that the M2SO4 (M: Li, Na) protection layer on NMC811 behaves as an artificial cathode electrolyte interphase (ACEI) that enhance the capacity retention by 25% during prolong cycling with respect to the untreated NMC811. Postmortem morphology studies reveal that the thin metal sulfates coatings remain on the cathode even after 100 cycles, while the untreated NCM811 shows severe morphological instabilities. Our study demonstrates that by simple chemical treatment of NMC811 can enhance its overall stability and cycling performance for the development of advanced high energy density Lithium-ion battery systems.

Rapid and accurate Gram differentiation is paramount as the first step of pathogen identification and antibiotics administration. However, the current method requires additional reagents, is time-consuming, and is operator dependent. Here we show the principle of tip enhanced Raman spectroscopy (TERS) can differentiate between Gram negative and positive species, by detecting the changes in tip-enhancement in the Raman scattering from the bacteria’s lipid-bilayer membrane, which specifically enhances Gram negative bacteria.

Interference lithography has proven to be a useful technique for generating periodic sub-diffraction limited nanostructures. Interference lithography can be implemented by exposing a photoresist polymer to laser light using a two-beam arrangement or a one-beam configuration based on a Lloyd’s Mirror Interferometer. For typical photoresist layers, an anti-reflection coating must be deposited on the substrate to prevent adverse reflections from cancelling the holographic pattern of the interfering beams. For silicon substrates, such coatings are typically multilayered and complex in composition. By thinning the photoresist layer to a thickness well below the quarter wavelength of the exposing beam, we demonstrate that interference gratings can be generated without an anti-reflection coating on the substrate. We used ammonium dichromate doped polyvinyl alcohol as the positive photoresist because it provides excellent pinhole free layers down to thicknesses of 40 nm, and can be cross-linked by a low-cost single mode 457 nm laser and etched in water. Gratings with a period of 320 nm and depth of 4 nm were realized, as well as a variety of morphologies depending on the photoresist thickness. This simplified interference lithography technique promises to be useful for generating periodic nanostructures with high fidelity and minimal substrate treatments.

Finding renewable energy sources is of paramount importance to meet the increasing global energy demand whilst minimizing the impact on the environment. The research community has focused on solar energy as it is endlessly available, and have ranked the methylammonium lead iodide (MAPbI3) as one of the most promising candidate amongst perovskite solar cells. Despite its high efficiency, the MAPbI3 is sensitive to humidity, light, and temperature, its instability affects primarily on the crystalline structure and eventually leads to degradation. Three crystalline structures are known for this material, orthorhombic, tetragonal, and cubic which exist in different temperatures. Here we report on several processes detected from laser excitation of MAPbI3 single crystal at ambient conditions. A phase transition from tetragonal to cubic phase was induced by excitation of over 15 mW laser power. The phases were characterized by LF-Raman and photoluminescence, taken simultaneously with the increase of exciting laser power and the spectral changes were assigned to the structural differences. In addition, Raman stimulation of iodine vapors signal was observed, those vapors were generated from the core of the focus wherein the highest temperature led to degradation. The stimulated Raman phenomenon was enabled due to the unique properties of the MAPbI3 single crystal and revealed viability to use this material for additional applications in other research fields.

Here we present the synthesis and optical characterization of a new amphiphilic cyanine dye, 1,1′-dioctadecane-3,3′-di(4-sulfobutyl)-5,5′,6,6′-tetrachloro-benzimidazolocarbo-cyanine (C18S4). C18S4 is a derivative of the heavily studied J-aggregating cyanine dye TDBC that was designed specifically for creating stable amphiphilic monolayers when spread at an air–water interface. Unlike TDBC, which readily J-aggregates in water, we show that C18S4 introduced into water tends to produce micelles with monomeric spectral properties and only exhibits strong J-aggregation after an emulsification procedure and a week of dye reorganization. When deposited on a Langmuir Blodgett (LB) trough, C18S4 forms a stable monolayer with a repeatable isotherm. Layers transferred via LB deposition to a functionalized glass substrate show pronounced J-aggregation, depending on the surface transfer pressure. Layers transferred at 35 mN/m present an intense narrow absorption spectrum peaked at λ =589 nm with FWHM=523 cm −1 (18 nm). The accompanying fluorescence shows a narrow spectrum with FWHM=332 cm −1 (11.5 nm) and a Stokes shift less than 1 nm. The ability to create J-aggregates of C18S4 via LB deposition provides control over the J-aggregation process of TDBC-like molecules and can ultimately lead to tuning the J-aggregate coupling for specific experiments and applications.

We present a new method for differentiating racemic crystals from enantiopure crystals. Recently, developments in optical filters have enabled the facile use of Raman spectroscopy to detect low-frequency vibrational (LFV) modes. Here, for the first time, we use Raman spectroscopy to characterize the LFV modes for crystalline organic materials composed of chiral molecules. The LF-Raman spectra of racemic and enantiopure crystals exhibit a significant variation, which we attribute to different hydrogen-bond networks in the chiral crystal structures. Across a representative set of amino acids, we observed that when comparing racemic versus enantiopure crystals, the available LFV modes and their relative scattering intensity are strong functions of side chain polarity. Thus, LF-Raman can be used as a method that is complementary to the currently used methods for characterizing crystal chirality due to simpler, faster, and more sensitive measurements, along with the small sample size required, which is limited by the laser-beam diameter in the focus.

The ability to confine excitons within monolayers has led to fundamental investigations of nonradiative energy transfer, super-radiance, strong light–matter coupling, high-efficiency light-emitting diodes, and recently lasers in lateral resonator architectures. Vertical cavity surface emitting lasers (VCSELs), in which lasing occurs perpendicular to the device plane, are critical for telecommunications and large-scale photonics integration, however strong optical self-absorption and low fluorescence quantum yields have thus far prevented coherent emission from a monolayer microcavity device. Here we show lasing from a monolayer VCSEL using a single molecule thick film of amphiphilic fluorescent dye, assembled via Langmuir–Blodgett deposition, as the gain layer. Threshold was observed when 5% of the molecules were excited (4.4 μJ/cm2). At this level of excitation, the optical gain in the monolayer exceeds 1056 cm–1. High localization of the excitons in the VCSEL gain layer can enhance their collective emis...

Phase separation occurs whenever a solvent leaves a solution of strongly incompatible polymers. This can happen in bulk and in films. Films can be tailored as substrates for multiple applications such as solar cells, surface catalysis, and antireflection coatings. In this study, polystyrene (PS) was dissolved with polyvinyl acetate (PVAc) in different ratios using chlorobenzene as the solvent. Thin films of different ratios of PS and PVAc were deposited on glass via spin coating. The deposited films were investigated for their morphology, strain, surface area, and Raman scattering. The incompatibility between the two polymers leads to the growth of roughened PVAc islands supported by the PS matrix. A down shift in the Raman PVAc signal was observed in the combined film as compared with a 100% PVAc film, which was attributed to the high strain of PVAc that grew as tips. As the PVAc concentration in the polymer blend increases, the porous regions in the film expand and the amount and height of PVAc tips increase as well, up to the point where the pores merge to create a uniform surface. The optimal ratio for the deposition of a uniformly roughened surface is 75% PVAc and 25% PS. For demonstrating a possible application, we applied the partially roughened surface as a substrate for surface-enhanced Raman scattering and demonstrated at least 500% increase in the signal intensity measured in roughened areas. This is explained by the rod effect from the PVAc tips.

Here we present characterization of solution and thin film properties of Lissamine rhodamine B sulfonyl didodecyl amine (LRSD), an amphiphilic derivative of rhodamine. LRSD was synthesized by functionalizing Lissamine rhodamine B sulfonyl chloride (LRSC) with didodecylamine via a straightforward sulfonylation reaction. LRSD's long alkane chains make it highly soluble in chloroform, with a marked increase in brightness compared to the starting material. LRSD is shown to form well-defined robust micelles in water, without the addition of a co-surfactant and stable monolayers at the air–water interface. The greater lipophilicity of LRSD also enables doping into non-polar polymeric host matrices such as polystyrene with less aggregation and hence higher fluorescence quantum yield than LRSC or even rhodamine B. The monolayers of LRSD were prepared via Langmuir–Blodgett deposition and showed shifts in the photoluminescence peak from 575 nm to 595 nm, as the surface pressure is varied from 3 mN/m to 11 mN/m.

All-oxide-based photovoltaics (PVs) encompass the potential for extremely low cost solar cells, provided they can obtain an order of magnitude improvement in their power conversion efficiencies. To achieve this goal, we perform a combinatorial materials study of metal oxide based light absorbers, charge transporters, junctions between them, and PV devices. Here we report the development of a combinatorial internal quantum efficiency (IQE) method. IQE measures the efficiency associated with the charge separation and collection processes, and thus is a proxy for PV activity of materials once placed into devices, discarding optical properties that cause uncontrolled light harvesting. The IQE is supported by high-throughput techniques for bandgap fitting, composition analysis, and thickness mapping, which are also crucial parameters for the combinatorial investigation cycle of photovoltaics. As a model system we use a library of 169 solar cells with a varying thickness of sprayed titanium dioxide (TiO2) as the window layer, and covarying thickness and composition of binary compounds of copper oxides (Cu-O) as the light absorber, fabricated by Pulsed Laser Deposition (PLD). The analysis on the combinatorial devices shows the correlation between compositions and bandgap, and their effect on PV activity within several device configurations. The analysis suggests that the presence of Cu4O3 plays a significant role in the PV activity of binary Cu-O compounds.

Recent developments in optical filters have enabled the facile use of Raman spectroscopy for detection of low frequency (LF) vibrational modes. LF-Raman spectroscopy offers fast and sensitive characterization of LF vibrations, and enables the measurement of single microcrystals and detection of defects. It is useful for probing intermolecular interactions in crystals, which are lower in energy, such as hydrogen bonds, shear modes, and breathing modes. Crystal excitation from multiple faces allows learning the orientation of intermolecular interactions, as polarization dependence varies with the polarizability of the interactions along the planes. Elucidating the orientations of the intermolecular interactions in organic crystals is essential for guiding the reactions or adsorption to a specific crystal face. In this study, we investigated the dependence of the LF-Raman signal intensity on the orientation of an organic single microcrystal of L-alanine. Three incident beam directions provided the orientations of the intermolecular interactions by analyzing the corresponding LF-Raman spectra. The signal intensity correlated well with the proximity between the incident beam&rsquo, s direction and the orientations of the intermolecular interactions. Excellent compatibility was found between the spectra and simulated orientations based on structural information.

Rapid and accurate detection of pathogens is paramount to human health. Spectroscopic techniques have been shown to be viable methods for detecting various pathogens. Enhanced methods of Raman spectroscopy can discriminate unique bacterial signatures; however, many of these require precise conditions and do not have in vivo replicability. Common biological detection methods such as rapid antigen detection tests have high specificity but do not have high sensitivity. Here we developed a new method of bacteria detection that is both highly specific and highly sensitive by combining the specificity of antibody staining and the sensitivity of spectroscopic characterization. Bacteria samples, treated with a fluorescent antibody complex specific to Streptococcus pyogenes, were volumetrically normalized according to their Raman bacterial signal intensity and characterized for fluorescence, eliciting a positive result for samples containing Streptococcus pyogenes and a negative result for those without. The normalized fluorescence intensity of the Streptococcus pyogenes gave a signal that is up to 16.4 times higher than that of other bacteria samples for bacteria stained in solution and up to 12.7 times higher in solid state. This method can be very easily replicated for other bacteria species using suitable antibody-dye complexes. In addition, this method shows viability for in vivo detection as it requires minute amounts of bacteria, low laser excitation power, and short integration times in order to achieve high signal.

Bismuth oxide nanoparticles of 12.1 ± 3.0 nm diameter were prepared by thermal decomposition of bismuth acetate dissolved in ethylene glycol in the presence of an oxidizing agent. Functionalization and stabilization of the hydrophobic Bi2O3 nanoparticles was accomplished by coating these core nanoparticles with human serum albumin (HSA), via a precipitation process. The formed Bi2O3/HSA core-shell nanoparticles were of 15.2 ± 3.5 nm diameter. Elemental analysis measurements indicated that the bismuth weight % of the Bi2O3/HSA core-shell nanoparticles is 72.9. The crystalline structure of these nanoparticles was examined by XRD. The radiopacity of these nanoparticles was demonstrated in vitro and in vivo by a CT scanner. In ovo and in vivo trials proved the safety of these Bi2O3/HSA core-shell nanoparticles. In the future, we plan to extend this study particularly for molecular imaging applications. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 101B: 131–138, 2013.

Pulsed laser deposition (PLD) is widely used in combinatorial material science, as it enables rapid fabrication of different composite materials. Nevertheless, this method was usually limited to small substrates, since PLD deposition on large substrate areas results in severe lateral inhomogeneity. A few technical solutions for this problem have been suggested, including the use of different designs of masks, which were meant to prevent inhomogeneity in the thickness, density, and oxidation state of a layer, while only the composition is allowed to be changed. In this study, a possible way to take advantage of the large scale deposition inhomogeneity is demonstrated, choosing an iron oxide PLD-deposited library with continuous compositional spread (CCS) as a model system. An Fe₂O₃-Nb₂O₅ library was fabricated using PLD, without any mask between the targets and the substrate. The library was measured using high-throughput scanners for electrical, structural, and optical properties. A decrease in electrical resistivity that is several orders of magnitude lower than pure α-Fe₂O₃ was achieved at ∼20% Nb-O (measured at 47 and 267 °C) but only at points that are distanced from the center of the PLD plasma plume. Using hierarchical clustering analysis, we show that the PLD inhomogeneity can be used as an additional degree of freedom, helping, in this case, to achieve iron oxide with much lower resistivity.

In this work, we investigate the properties of an organic distributed feedback laser as the concentration of the gain material in the waveguide core is varied across two orders of magnitude, from 5% down to 0.025%. The laser dye DCJTB (4-(Dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidin-9-enyl-vinyl)-4H-pyran) incorporated into a PVK (poly(9-vinylcarbazole)) host matrix provided the gain. The composite layer of PVK:DCJTB was spin-cast onto a silica grating with second order periodicity, and upon nanosecond optical excitation lasing was generated in the wavelength range of 600 nm. The threshold pulse energy for achieving lasing increased as the concentration of DCJTB was reduced, however the threshold excitation density quantified in terms of number of excited molecules per unit area remained nearly constant at 1.3×1013 molecules/cm2. In contrast, the relative slope efficiency for lasing decreased considerably as the gain concentration was reduced. We show that this effect can not be explained by a standard 4-level lasing model, but rather that it is due to optically induced charge separation for the DCJTB molecules situated in the PVK host matrix. Our findings suggest that fast charge separation and long back recombination times can be a significant factor in limiting further reduction of the gain concentration in organic DFB lasers.

In this chapter we describe the synthesis of iodinated homopolymeric radiopaque nanoparticles of 28.9 ± 6.3 nm diameter prepared by emulsion polymerization of 2-methacryloyloxyethyl(2,3,5-triiodobenzoate) (MAOETIB). These nanoparticles dispersed in aqueous continuous phase tend to agglomerate in concentration above 0.3%. The agglomeration rate increases as the concentration of the nanoparticles in the aqueous phase rises, and prevents thereby the in vivo use as contrast agent for medical X-ray imaging. This limitation was solved by synthesis of copolymeric iodinated nanoparticles of 25.5 ± 4.2 nm diameter, via emulsion copolymerization of MAOETIB in the presence of a low concentration of glycidyl methacrylate (GMA). The surface of the resulting copolymeric nanoparticles is far more hydrophilic than that of the polyMAOETIB (PMAOETIB) nanoparticles. Therefore, P(MAOETIB-GMA) nanoparticles are significantly more stable against agglomeration in aqueous continuous phase. After intravenous injection of the P(MAOETIB-GMA) nanoparticles dispersed in 5% dextrose aqueous solution into rats and mice (including those with a liver cancer model) CT-imaging revealed a significant enhanced visibility of the blood pool for 30 min after injection. Later, lymph nodes, liver and spleen strongly enhanced due to nanoparticles uptake by the reticuloendothelial system. This favorably enabled the differentiation of cancerous from healthy liver tissue and suggests our particles for tumor imaging in liver and lymph nodes. Keywords: iodinated particles; contrast agents; core–shell nanoparticles; microparticles; computed tomography; X-ray

Interference lithography has proven to be a useful technique for generating periodic sub-diffraction limited nanostructures. Interference lithography can be implemented by exposing a photoresist polymer to laser light using a two-beam arrangement or more simply a one beam configuration based on a Lloyd's Mirror Interferometer. For typical photoresist layers, an anti-reflection coating must be deposited on the substrate to prevent adverse reflections from cancelling the holographic pattern of the interfering beams. For silicon substrates, such coatings are typically multilayered and complex in composition. By thinning the photoresist layer to a thickness well below the quarter wavelength of the exposing beam, we demonstrate that interference gratings can be generated without an anti-reflection coating on the substrate. We used ammonium dichromate doped polyvinyl alcohol as the positive photoresist because it provides excellent pinhole free layers down to thicknesses of 40 nm, and can be cross-linked by a l...

Objectives Embolization therapy is gaining importance in the treatment of malignant lesions, and even more in benign lesions. Current embolization materials are not visible in imaging modalities. However, it is assumed that directly visible embolization material may provide several advantages over current embolization agents, ranging from particle shunt and reflux prevention to improved therapy control and follow-up assessment. X-ray- as well as magnetic resonance imaging (MRI)-visible embolization materials have been demonstrated in experiments. In this study, we present an embolization material with the property of being visible in more than one imaging modality, namely MRI and x-ray/computed tomography (CT). Characterization and testing of the substance in animal models was performed. Materials and methods To reduce the chance of adverse reactions and to facilitate clinical approval, materials have been applied that are similar to those that are approved and being used on a routine basis in diagnostic imaging. Therefore, x-ray-visible Iodine was combined with MRI-visible Iron (Fe3O4) in a macroparticle (diameter, 40-200 μm). Its core, consisting of a copolymerized monomer MAOETIB (2-methacryloyloxyethyl [2,3,5-triiodobenzoate]), was coated with ultra-small paramagnetic iron oxide nanoparticles (150 nm). After in vitro testing, including signal to noise measurements in CT and MRI (n = 5), its ability to embolize tissue was tested in an established tumor embolization model in rabbits (n = 6). Digital subtraction angiography (DSA) (Integris, Philips), CT (Definition, Siemens Healthcare Section, Forchheim, Germany), and MRI (3 Tesla Magnetom Tim Trio MRI, Siemens Healthcare Section, Forchheim, Germany) were performed before, during, and after embolization. Imaging signal changes that could be attributed to embolization particles were assessed by visual inspection and rated on an ordinal scale by 3 radiologists, from 1 to 3. Histologic analysis of organs was performed. Results Particles provided a sufficient image contrast on DSA, CT (signal to noise [SNR], 13 ± 2.5), and MRI (SNR, 35 ± 1) in in vitro scans. Successful embolization of renal tissue was confirmed by catheter angiography, revealing at least partial perfusion stop in all kidneys. Signal changes that were attributed to particles residing within the kidney were found in all cases in all the 3 imaging modalities. Localization distribution of particles corresponded well in all imaging modalities. Dynamic imaging during embolization provided real-time monitoring of the inflow of embolization particles within DSA, CT, and MRI. Histologic visualization of the residing particles as well as associated thrombosis in renal arteries could be performed. Visual assessment of the likelihood of embolization particle presence received full rating scores (153/153) after embolization. Conclusions Multimodal-visible embolization particles have been developed, characterized, and tested in vivo in an animal model. Their implementation in clinical radiology may provide optimization of embolization procedures with regard to prevention of particle misplacement and direct intraprocedural visualization, at the same time improving follow-up examinations by utilizing the complementary characteristics of CT and MRI. Radiation dose savings can also be considered. All these advantages could contribute to future refinements and improvements in embolization therapy. Additionally, new approaches in embolization research may open up.

Recently we described iodinated homopolymeric radiopaque nanoparticles of 28.9+/-6.3 nm dry diameter synthesized by emulsion polymerization of 2-methacryloyloxyethyl(2,3,5-triiodobenzoate) (MAOETIB). The nanoparticle aqueous dispersion, however, was not stable and tended to agglomerate, particularly at weight concentration of dispersed nanoparticles above approximately 0.3%. The agglomeration rate increases as the concentration of nanoparticles in aqueous phase rises and prevents the potential in vivo use as contrast agent for medical X-ray imaging. Here we describe efforts to overcome this limitation by synthesis of iodinated copolymeric nanoparticles of 25.5+/-4.2 nm dry diameter, by emulsion copolymerization of the monomer, MAOETIB, with a low concentration of glycidyl methacrylate (GMA). The surface of resulting copolymeric nanoparticles is far more hydrophilic than that of polyMAOETIB (PMAOETIB) nanoparticles. Therefore, P(MAOETIB-GMA) nanoparticles are significantly more stable against agglomeration in aqueous continuous phase. After intravenous injection of P(MAOETIB-GMA) nanoparticles in rats and mice (including those with a liver cancer model) CT-imaging revealed a significant enhanced visibility of the blood pool for 30 min after injection. Later, lymph nodes, liver and spleen strongly enhanced due to nanoparticle uptake by the reticuloendothelial system. This favorably enabled the differentiation of cancerous from healthy liver tissue and suggests our particles for tumor imaging in liver and lymph nodes.