Silica- and alkoxysilane-coated ultrasmall superparamagnetic iron oxide particles: a promising tool to label cells for magnetic resonance imaging

In this study silica- and alkoxysilane-coated ultrasmall superparamagnetic iron oxide (USPIO) particles were synthesized, and their ability to label immortalized progenitor cells for magnetic resonance imaging (MRI) was compared. USPIO particles were synthesized by coprecipitation of ferric and ferrous salts. Subsequently, the particles were coated with silica, (3-aminopropyl)trimethoxysilane (APTMS), and [N-(2-aminoethyl)-3-aminopropyl]trimethoxysilane (AEAPTMS). The size of the USPIO particles was about 10 nm without a significant increase in diameter after coating. The highest T2 relaxivity was achieved for silica-coated USPIO particles, 339.80 +/- 0.22 s-1 mM-1, as compared with APTMS- and AEAPTMS-coated ones, reaching 134.40 +/- 0.01 and 84.79 +/- 0.02 s-1 mM-1, respectively. No toxic effects on the cells could be detected by trypan blue, TUNEL, and MTS assays. Uptake of USPIO particles was evaluated by Prussian blue staining, transmission electron microscopy, T2-MR relaxometry, and mass spectrometry. It was found that cell uptake of the different USPIO particles increased for longer incubation times and higher doses. Maximum cellular iron concentrations of 42.1 +/- 4.0 pg/cell (silica-coated USPIO particles), 37.1 +/- 3.5 pg/cell (APTMS-coated USPIO particles), and 32.7 +/- 4.0 pg/cell (AEAPTMS-coated USPIO particles) were achieved after incubation of the cells with USPIO particles at a dose of 3 micromol/mL for 6 h. The decrease of the T2 relaxation time of the cell pellets was most pronounced for cells incubated with silica-coated USPIO particles followed by APTMS- and AEAPTMS-coated particles, respectively. In gelatin gels even small clusters of labeled cells were detected by 1.5 T MRI, and significant changes in the T2 relaxation times of the gels were determined for 10000 labeled cells/mL for all particles. In summary, as compared with APTMS- and AEAPTMS-coated particles, silica-coated USPIO particles provide the highest T2 relaxivity and most effectively reduce the T2 relaxation time of immortalized progenitor cells after internalization. This suggests silica-coated USPIO particles are most suited for cell labeling approaches in MRI.     

Synthesis and characterization of silyldichloramines, their reactions with F- ions, instability of N2Cl2 and NCl2-, and formation of NCl3

Only two silyldichloramines, (C6H5)3SiNCl2 and (CH3)3SiNCl2, have been reported in the literature. The synthesis of the former was successfully repeated, and its structure was established by single-crystal X-ray diffraction and vibrational spectroscopy. Attempts to prepare (CH3)3SiNCl2 were unsuccessful; however, a new trialkylsilyldichloramine, t-BuMe2Si-NCl2, was prepared and characterized by Raman and multinuclear NMR spectroscopy. The reaction of t-BuMe2SiNCl2 with (CH3)4NF in CHF3 solution at -78 degrees C, followed by removal of all volatile products at -30 degrees C, produced the expected t-BuMe2SiF byproduct and a white solid consisting of NCl3 absorbed on Me4NCl. The NCl3 could be reversibly desorbed from the substrate and was identified as a neat liquid at room temperature by Raman spectroscopy. The observed final reaction products are consistent with the formation of an unstable N(CH3)4+NCl2- intermediate which decomposes to N(CH3)4+Cl- and NCl molecules which can dimerize to N2Cl2. Theoretical calculations confirm that NCl2- can readily lose Cl- and that N2Cl2 also possesses a low barrier toward loss of N2 to give chlorine atoms and, thus, can account for the formation of NCl3.     

Organometallic Heterocubane Clusters with Co–O and Co–S Framework

The reaction of [{(η⁵-Me₅C₅)Co}₂(μ-η⁶:η⁶-toluene)] with water under different conditions leads to formation of the clusters [{(η⁵-Me₅C₅)Co}₃(μ₃-O)₂] (1), [{(η⁵-Me₅C₅)Co}₄(μ₃-OH)₄] (2) and [{(η⁵-Me₅C₅)Co}₃(μ₃-OH)₄]₂Co (3), whereas its reaction with hydrogen sulfide leads to [{(η⁵-Me₅C₅)Co}₃(μ₃-S)₄]Co(μ₃-S)₂[(η⁵-Me₅C₅)Co]₂ · Et₂O (4). 1, 2 and 4 were characterized by single crystal X-ray diffraction. 1 is composed of a central Co₃O₂ unit, with two O^2- units in an apical postion. The three cobalt atoms form a regular triangle with Co–Co distances of 2.438(2) Å, and the two oxygen atoms are located in apical positions of the triangular arrangement. The pentamethylcyclopentadienyl (Cp*) ligands are terminally bonded to the Co atoms in a η⁵-fashion. The Co and O atoms of 2 form a cubane-type Co₄O₄ cluster, with η⁵-bonded Cp* ligands. The central unit of 3 consists of a Co₇O₈ double cubane framework. Two Co₄O₄ cluster sharing a common corner (Co atom). Each of the other six Co atoms of the double cubane bound terminally a Cp* ligand. 4 is composed of a [{(η⁵-Me₅C₅)Co }₂(μ₃-S)₄](μ₃-S)₂[(η⁵-Me₅C₅)Co]₂ and an ether molecule. 4 contains a central Co₄S₄ cubane-like unit. One of the four Co atoms is bonded via two μ₃-S atoms to two additional (η⁵-Cp*Co) units. The other three Co atoms are η⁵-coordinated to a Cp* ligand.     

Model Studies on the Ozone-Mediated Synthesis of Cobalt Oxide Nanoparticles from Dicobalt Octacarbonyl in Ionic Liquids

Low-temperature synthesis in ionic liquids (ILs) offers an efficient route for the preparation of metal oxide nanomaterials with tailor-made properties in a water-free environment. In this work, we investigated the role of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [C₄C₁Pyr][NTf₂] in the synthesis of cobalt oxide nanoparticles from the molecular precursor Co₂(CO)₈ with ozone. We performed a model study in ultra-clean, ultrahigh vacuum (UHV) conditions by infrared reflection absorption spectroscopy (IRAS) using Au(111) as a substrate. Exposure of the pure precursor to ozone at low temperatures results in the oxidation of the first layers, leading to the formation of a disordered Co_xO_y passivation layer. Similar protection to ozone is also achieved by deposition of an IL layer onto a precursor film prior to ozone exposure. With increasing temperature, the IL gets permeable for ozone and a cobalt oxide film forms at the IL/precursor interface. We show that the interaction with the IL mediates the oxidation and leads to a more densely packed Co_xO_y film compared to a direct oxidation of the precursor.     

Towards DNA-Encoded Micellar Chemistry: DNA-Micelle Association and Environment Sensitivity of Catalysis

The development of DNA-compatible reaction methodologies is a central theme to advance DNA-encoded screening library technology. Recently, we were able to show that sulfonic acid-functionalized block copolymer micelles facilitated Brønsted acid-promoted reactions such as the Povarov reaction on DNA-coupled starting materials with minimal DNA degradation. Here, the impact of polymer composition on micelle shape, and reaction conversion was investigated. A dozen sulfonic acid-functionalized block copolymers of different molar mass and composition were prepared by RAFT polymerization and were tested in the Povarov reaction, removal of the Boc protective group, and the Biginelli reaction. The results showed trends in the polymer structure-micellar catalytic activity relationship. For instance, micelles composed of block copolymers with shorter acrylate ester chains formed smaller particles and tended to provide faster reaction kinetics. Moreover, fluorescence quenching experiments as well as circular dichroism spectroscopy showed that DNA-oligomer-conjugates, although highly water-soluble, accumulated very effectively in the micellar compartments, which is a prerequisite for carrying out a DNA-encoded reaction in the presence of polymer micelles.     

Benefits of working capital sharing in supply chains

Supply chain finance and working capital management are important avenues to reduce supply chain costs. Small suppliers may not have sufficient working capital to finance their operations and efficiently supply their customers. We develop a model that captures the fundamental aspects of financial and operational planning in a two-stage supply chain, with both strong and weak members. A strong member can negotiate for more favorable financing rates, more advantageous payment terms, and shorter lead times than a weaker member. We investigate two working capital allocation scenarios. In the dedicated working capital allocation scenario, the members of the supply chain each have their own working capital. In the joint working capital allocation scenario, the members of the supply chain have a joint pool of working capital. Our results demonstrate significant benefits when the members of the supply chain share the working capital. We also show that extending payment delays to a supplier upstream results in higher overall supply chain costs.     

Reduced C*-algebras of Fell bundles over inverse semigroups

We construct a weak conditional expectation from the section C*-algebra of a Fell bundle over a unital inverse semigroup to its unit fibre. We use this to define the reduced C*-algebra of the Fell bundle. We study when the reduced C*-algebra for an inverse semigroup action on a groupoid by partial equivalences coincides with the reduced groupoid C*-algebra of the transformation groupoid, giving both positive results and counterexamples.     

Numerical investigation of the effective Skempton coefficient in fluid-saturated fractured rock

Characterization of hydro-mechanical processes in reservoir rocks is an essential issue for many geo investigations such as characterization of subsurface fluid flow or geothermal exploitation. For geothermal applications, the role of fractures as storage and transport components of a hydraulic system are highly important. In the present contribution we focus on investigating the effective Skempton coefficient of a damaged porous rock analyzing a modified Cryer problem, which provides a simple model of a porous rock containing a storage and transport pat. The effective Skempton coefficient is defined as the ratio of the increase in mean pore pressure induced by change in confining pressure for undrained boundary conditions. Using approaches from computational homogenization, we evaluate the confining pressure as the negative volume average of the total mean stress. Similarly, we compute the effective fluid pressure in terms of the volume-averaged fluid pressure in the rocks. We compare the numerical results to those from typical experiments and highlight the problems with the latter. The proposed concept for determination of an effective Skempton coefficient based on numerically evaluated volume averages helps to generate a better understanding of the process-inherent constituents. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Equilibrium and nonequilibrium dynamics of the sub-Ohmic spin-boson model

Employing the nonperturbative numerical renormalization group method, we study the dynamics of the spin-boson model, which describes a two-level system coupled to a bosonic bath with a spectral density J(omega) proportional to omega(s). We show that, in contrast with the case of Ohmic damping, the delocalized phase of the sub-Ohmic model cannot be characterized by a single energy scale only, due to the presence of a nontrivial quantum phase transition. In the strongly sub-Ohmic regime, s<1, weakly damped coherent oscillations on short time scales are possible even in the localized phase--this is of crucial relevance, e.g., for qubits subject to electromagnetic noise.     

Microresonator array for high-resolution spectroscopy

We investigated the properties of an array of spherical microresonators used as a miniaturized high-resolution spectroscopic device. Sixteen spherical microspheres made from polymethyl methacrylate were placed on a microscope slide serving as an optical wave guide. Light of a tunable narrowband laser source was coupled into this slide so that an evanescent wave was excited on the topside of the slide, where the resonators were placed. This evanescent field generated a particular intensity pattern in the array that depended sensitively on the wavelength. After calibration, that pattern was recorded by a CCD camera and used to identify the wavelength with a resolution of R ~ lambda/Deltalambda = 7 x 10(4).