Manganese-enhanced magnetic resonance microscopy of mineralization

Paramagnetic manganese (II) can be employed as a calcium surrogate to sensitize magnetic resonance microscopy (MRM) to the processing of calcium during bone formation. At high doses, osteoblasts can take up sufficient quantities of manganese, resulting in marked changes in water proton T(1), T(2) and magnetization transfer ratio values compared to those for untreated cells. Accordingly, inductively coupled plasma mass spectrometry (ICP-MS) results confirm that the manganese content of treated cell pellets was 10-fold higher than that for untreated cell pellets. To establish that manganese is processed like calcium and deposited as bone, calvaria from the skull of embryonic chicks were grown in culture medium supplemented with 1 mM MnCl(2) and 3 mM CaCl(2). A banding pattern of high and low T(2) values, consistent with mineral deposits with high and low levels of manganese, was observed radiating from the calvarial ridge. The results of ICP-MS studies confirm that manganese-treated calvaria take up increasing amounts of manganese with time in culture. Finally, elemental mapping studies with electron probe microanalysis confirmed local variations in the manganese content of bone newly deposited on the calvarial surface. This is the first reported use of manganese-enhanced MRM to study the process whereby calcium is taken up by osteoblasts cells and deposited as bone.     

Selective Uptake of Cylindrical Poly(2‐Oxazoline) Brush‐AntiDEC205 Antibody‐OVA Antigen Conjugates into DEC‐Positive Dendritic Cells and Subsequent T‐Cell Activation

To achieve specific cell targeting by various receptors for oligosaccharides or antibodies, a carrier must not be taken up by any of the very many different cells and needs functional groups prone to clean conjugation chemistry to derive well‐defined structures with a high biological specificity. A polymeric nanocarrier is presented that consists of a cylindrical brush polymer with poly‐2‐oxazoline side chains carrying an azide functional group on each of the many side chain ends. After click conjugation of dye and an anti‐DEC205 antibody to the periphery of the cylindrical brush polymer, antibody‐mediated specific binding and uptake into DEC205⁺‐positive mouse bone marrow‐derived dendritic cells (BMDC) was observed, whereas binding and uptake by DEC205^? negative BMDC and non‐DC was essentially absent. Additional conjugation of an antigen peptide yielded a multifunctional polymer structure with a much stronger antigen‐specific T‐cell stimulatory capacity of pretreated BMDC than application of antigen or polymer–antigen conjugate.     

A comparison of conformational energies calculated by several molecular mechanics methods

Several commonly used molecular mechanics force fields have been tested for accuracy in conformational energy calculations. Differences in performance between the force fields are discussed for different classes of structures. MMFF93 and force fields based on the MM2 or MM3 functional form are found to perform significantly better than other force fields in the test, with average conformational energy errors around 0.5 kcal/mol. CFF91 also reaches this accuracy for the subset in which fully determined parameters are used, but it doubles the overall error due to use of estimated parameters. Harmonic force fields generally have average errors exceeding 1 kcal/mol. Factors influencing accuracy are identified and discussed. © 1996 by John Wiley & Son s, Inc.     

Codimension-two border collision bifurcation in a two-class growth model with optimal saving and switch in behavior

Nonlinear Dynamics - We consider a two-class growth model with optimal saving and switch in behavior. The dynamics of this model is described by a two-dimensional (2D) discontinuous map. We obtain...     

Multiscale Approach to the Study of the Electronic Properties of Two Thiophene Curcuminoid Molecules

We studied the electronic and conductance properties of two thiophene–curcuminoid molecules, 2‐thphCCM ( 1 ) and 3‐thphCCM ( 2 ), in which the only structural difference is the position of the sulfur atoms in the thiophene terminal groups. We used electrochemical techniques as well as UV/Vis absorption studies to obtain the values of the HOMO–LUMO band gap energies, showing that molecule 1 has lower values than 2 . Theoretical calculations show the same trend. Self‐assembled monolayers (SAMs) of these molecules were studied by using electrochemistry, showing that the interaction with gold reduces drastically the HOMO–LUMO gap in both molecules to almost the same value. Single‐molecule conductance measurements show that molecule 2 has two different conductance values, whereas molecule 1 exhibits only one. Based on theoretical calculations, we conclude that the lowest conductance value, similar in both molecules, corresponds to a van der Waals interaction between the thiophene ring and the electrodes. The one order of magnitude higher conductance value for molecule 2 corresponds to a coordinate (dative covalent) interaction between the sulfur atoms and the gold electrodes.     

Effects of the physicochemical properties of titanium dioxide nanoparticles, commonly used as sun protection agents, on microvascular endothelial cells

Until now, the potential effects of titanium dioxide (TiO₂) nanoparticles on endothelial cells are not well understood, despite their already wide usage. Therefore, the present work characterizes six TiO₂ nanoparticle samples in the size range of 19 × 17 to 87 × 13 nm, which are commonly present in sun protection agents with respect to their physicochemical properties (size, shape, ζ-potential, agglomeration, sedimentation, surface coating, and surface area), their interactions with serum proteins and biological impact on human microvascular endothelial cells (relative cellular dehydrogenase activity, adenosine triphosphate content, and monocyte chemoattractant protein-1 release). We observed no association of nanoparticle morphology with the agglomeration and sedimentation behavior and no variations of the ζ-potential (?14 to ?19 mV) in dependence on the surface coating. In general, the impact on endothelial cells was low and only detectable at concentrations of 100 μg/ml. Particles containing a rutile core and having rod-like shape had a stronger effect on cell metabolism than those with anatase core and elliptical shape (relative cellular dehydrogenase activity after 72 h: 60 vs. 90 %). Besides the morphology, the nanoparticle shell constitution was found to influence the metabolic activity of the cells. Upon cellular uptake, the nanoparticles were localized perinuclearly. Considering that in the in vivo situation endothelial cells would come in contact with considerably lower nanoparticle amounts than the lowest-observable adverse effects level (100 μg/ml), TiO₂ nanoparticles can be considered as rather harmless to humans under the investigated conditions.     

The application of MAS recoupling methods in the intermediate motional regime

We present investigations concerning the effect of molecular motions on the experimental timescale upon the recoupling of anisotropic interactions under magic-angle spinning conditions. An approach for the efficient simulation of spin dynamics occurring during complex pulse sequences, based on a linearization of the general solution of the stochastic Liouville-von Neumann equation, was developed. Using (13)C CSA recoupling of the methyl carbon in dimethylsulfon as a sample interaction, we observed a characteristic signal decay under recoupling upon entering the intermediate motional regime, which can be well described by an apparent transverse relaxation time, T(2)(rcpl). This quantity does not depend on the spinning frequency to a first approximation. Specific recoupling experiments, namely the measurement of tensor parameters by spinning sideband analysis, and the determination of rate constants with the CODEX experiment, are discussed with respect to possibilities and limits of their application in the intermediate motional regime. Important conclusions are drawn with regards to the limited applicability of popular recoupling methods like REDOR to samples exhibiting intermediate mobility.