Primitive model electrolytes in the near and far field: Decay lengths from DFT and simulations.

Inspired by recent experimental observations of anomalously large decay lengths in concentrated electrolytes, we revisit the Restricted Primitive Model (RPM) for an aqueous electrolyte. We investigate the asymptotic decay lengths of the one-body ionic density profiles for the RPM in contact with a planar electrode using classical Density Functional Theory (DFT) and compare these with the decay lengths of the corresponding two-body correlation functions in bulk systems, obtained in previous Integral Equation Theory (IET) studies. Extensive Molecular Dynamics (MD) simulations are employed to complement the DFT and IET predictions. Our DFT calculations incorporate electrostatic interactions between the ions using three different (existing) approaches: one is based on the simplest mean-field treatment of Coulomb interactions (MFC), while the other two employ the Mean Spherical Approximation (MSA). The MSAc invokes only the MSA bulk direct correlation function, whereas the MSAu also incorporates the MSA bulk internal energy. Although MSAu yields profiles that are in excellent agreement with MD simulations in the near field, in the far field, we observe that the decay lengths are consistent between IET, MSAc, and MD simulations, whereas those from MFC and MSAu deviate significantly. Using DFT, we calculated the solvation force, which relates directly to surface force experiments. We find that its decay length is neither qualitatively nor quantitatively close to the large decay lengths measured in experiments and conclude that the latter cannot be accounted for by the primitive model. The anomalously large decay lengths found in surface force measurements require an explanation that lies beyond primitive models.

Tension and stiffness of the hard sphere crystal-fluid interface.

A combination of fundamental measure density functional theory and Monte Carlo computer simulation is used to determine the orientation-resolved interfacial tension and stiffness for the equilibrium hard-sphere crystal-fluid interface. Microscopic density functional theory is in quantitative agreement with simulations and predicts a tension of 0.66k(B)T/σ(2) with a small anisotropy of about 0.025k(B)T and stiffnesses with, e.g., 0.53k(B)T/σ(2) for the (001) orientation and 1.03k(B)T/σ(2) for the (111) orientation. Here k(B)T is denoting the thermal energy and σ the hard-sphere diameter. We compare our results with existing experimental findings.

Towing, breathing, splitting, and overtaking in driven colloidal liquid crystals.

The nonequilibrium response of a colloidal liquid-crystalline nematic phase to an external aligning field, which rotates in a plane, is explored by dynamical fundamental measure density-functional theory. Depending on the drive frequency, different dynamical states are found, which are characterized by towing and overtaking of the nematic director by the field as well as by breathing and dynamical splitting of the orientational distribution peak. This complex response can be exploited for smart optical switching and mixing devices.

Free energies, vacancy concentrations, and density distribution anisotropies in hard-sphere crystals: a combined density functional and simulation study.

We perform a comparative study of the free energies and the density distributions in hard-sphere crystals using Monte Carlo simulations and density functional theory (employing Fundamental Measure functionals). Using a recently introduced technique [T. Schilling and F. Schmid, J. Chem. Phys. 131, 231102 (2009)] we obtain crystal free energies to a high precision. The free energies from fundamental measure theory are in good agreement with the simulation results and demonstrate the applicability of these functionals to the treatment of other problems involving crystallization. The agreement between fundamental measure theory and simulations on the level of the free energies is also reflected in the density distributions around single lattice sites. Overall, the peak widths and anisotropy signs for different lattice directions agree, however, it is found that fundamental measure theory gives slightly narrower peaks with more anisotropy than seen in the simulations. Among the three types of fundamental measure functionals studied, only the White Bear II functional [H. Hansen-Goos and R. Roth, J. Phys.: Condens. Matter 18, 8413 (2006)] exhibits sensible results for the equilibrium vacancy concentration and a physical behavior of the chemical potential in crystals constrained by a fixed vacancy concentration.

Fundamental measure density functional theory for hard spherocylinders in static and time-dependent aligning fields.

The recently developed fundamental measure density functional theory (Hansen-Goos and Mecke 2009 Phys. Rev. Lett. 102 018302) for an inhomogeneous anisotropic hard body fluid is used as a basic ingredient in treating the Brownian dynamics of hard spherocylinders. After discussing the relevance of a free parameter in the fundamental measure density functional for the isotropic-nematic transition in equilibrium, we discuss the equilibrium phase behaviour of hard spherocylinders in a static external potential which couples only to the orientations. For external potentials favouring rod orientations along the poles of the unit sphere, there is a well-known paranematic-nematic transition which ceases to exist above a threshold of the strength V(0) of the external potential. However, when orientations along the equator are more favoured, in the plane of the potential energy V(0) and density, there is a phase transition from paranematic to nematic for any strength, which becomes second order above a critical threshold of V(0). The full equilibrium phase diagram in the V(0)-density plane is computed for a fixed rod aspect ratio of 5. For the equatorial cases, strength V(0) is then oscillating in time and dynamical density functional theory is used to compute the evolution of the orientational distribution. A subtle resonance for increasing oscillation frequencies is detected if the oscillating V(0) crosses the paranematic-nematic phase transition.

Characterisation of steroid receptor expression in the human prostate carcinoma cell line 22RV1 and quantification of androgen effects on mRNA regulation of prostate-specific genes.

In this study, the effect of natural androgens on the expression of androgen-regulated genes in the human prostate carcinoma cell line 22RV1 was characterised. To clarify the usefulness of the cells for in vitro studies concerning activation of androgen responsive genes by various steroidal compounds steroid receptor expression patterns had to be characterised intensively. Expression of androgen receptor (AR), estrogen receptor alpha (ERalpha) and beta (ERbeta), progestin receptor (PR) and glucocorticoid receptor alpha and beta was investigated by the means of RT-PCR, immunocytochemistry, ligand binding or Western blot. 22RV1 cells were proved to express androgen receptor and less glucocorticoid receptor beta on mRNA level. The confirmed mutation of the androgen receptor at codon H874 slightly apart from the steroid binding pocket seemed not to cause alteration of natural steroid hormone binding. mRNA expression of all progestin and estrogen receptor isoforms as well as glucocorticoid receptor alpha could not be detected. To study functional relevance of above-mentioned findings nine androgen-regulated genes were chosen to characterise the cell line and to determine androgenic effects using highly sensitive real-time RT-PCR. Addition of the three natural steroids dihydrotestosterone (DHT), testosterone, and 19-nortestosterone significantly influenced mRNA expression profiles. All compounds under study showed clear time-dependent and androgen-specific effects on transcriptional level. The results demonstrate that the cultivated human prostate carcinoma epithelial cells have a hormonal sensitivity correlated with the presence of specific receptors and can, therefore, serve as a selective model to study hormone action.

Characterisation of gene expression patterns in 22RV1 cells for determination of environmental androgenic/antiandrogenic compounds.

Alteration of androgen receptor function due to hormonally active compounds in the environment, may be responsible for impaired reproductive function in aquatic wildlife. Based on human prostate carcinoma 22RV1 cells, a cell culture expression system was established to test effects of putative androgenic/antiandrogenic compounds on endogenous gene expression. 22RV1 cells were shown to express human androgen receptor, but not human progestin (hPR) or human oestrogen receptor (hER) alpha and beta. Six androgen-regulated genes (ARGs) were chosen to determine androgenic/antiandrogenic action using highly sensitive real-time RT-PCR. Results showed that gene expression is altered in a time-dependent manner. After stimulation of cells by DHT (10nM), synthetic androgen R1881 (1 nM), or organic pesticides (difenoconazole, fentinacetate, tetramethrin) TMPRSS2 mRNA expression was down-regulated by the factor 0.6 after 24h of DHT treatment. Similar results were obtained when cells were assayed for mRNA expression of PSA after fentinacetate and R1881 stimulation. In contrast, TMPRSS2 expression was up-regulated by the factor 0.9 when cells were stimulated by tetramethrin. Final goal of the work is a sensitive determination of differential gene expression by different compounds under study, achievement of substance-specific expression patterns and function related analysis of potential androgens/antiandrogens.

[Total ulnar nerve paralysis due to acute traumatic aneurysm at the forearm]. / Komplette Parese des Nervus ulnaris durch ein traumatisches Aneurysma - Wiederherstellung der Nervenfunktion durch rechtzeitige Neurolyse.

We are reporting a case of complete ulnar nerve paralysis due to compression from a false aneurysm located in the distal forearm. The aneurysm developed after the patient stabbed himself with a meat hook. The ulnar paralysis developed after a 14-day period of latency. The diagnosis was made using detailed patient history, clinical examination, and a sonogram. Early surgical decompression of the nerve led to complete restitution of all functions.

[The surface roughness of orthodontic wires--a laser optical and profilometric study]. / Die Oberflächenrauheit orthodontischer Drähte--eine laseroptische und profilometrische Untersuchung.

The surface roughness of orthodontic wires is an essential factor that determines the effectiveness of arch guided tooth movement. Using the nondestructive technique of laser specular reflectance, the surface roughness of 11 nickel titanium orthodontic wires and a standard steel as well as a beta-titanium wire was measured. The results were compared with the results from surface profilometry. The smoothest wire, standard steel Hi-T, has an optical roughness of 0.10 microns, while the roughness from profilometry reached a value of 0.06 microns. The titanium molybdenum wire has an optical as well as a profilometric roughness of about 0.20 microns, while the roughness of the NiTi wires ranges from 0.10 microns to 1.30 microns. As the surface roughness not only influences the effectiveness of sliding mechanics, but also the corrosion behaviour and aesthetics, the manufacturers of orthodontic wires are asked to improve the surface quality of their products.

Conformational analysis of the dinucleotides 5'-methylphospho-N6-dimethyladenylyl-uridine (mpm62A-U) and 5'methylphospho-uridylyl-N6-dimethyladenosine (mpU-m62A) and of the trinucleotide U-m62A-U. A nuclear magnetic resonance and circular dichroic study.

NMR and CD studies were carried out on the dinucleotides 5'-methylphospho-N6-dimethyladenylyl-uridine (mpm62-U) and 5'-methylphospho-uridylyl-N6-dimethyladenosine (mpU-m62A) and on the trinucleotide U-m62A-U. A detailed comparison is given of the conformational features of mpm62A-U and mpU-m62A with the corresponding 5'-nonphosphorylated dinucleotides m62A-U and U-m62A, respectively. The behaviour of the trinucleotide U-m62A-U is compared with the properties of the constituent dinucleotides U-m62A and mpm62A-U. Chemical-shift and CD data were used to determine the amount of stacking interactions. For each compound NMR spectra were recorded at two or three sample concentrations in order to separate intermolecular and intramolecular base-base interactions. The coupling constants of the ribose ring are interpreted in terms of the N/S equilibrium, and population distributions along the backbone angles beta, gamma and epsilon are presented. The combined data indicate a strong similarity between mpm62A-U and m62A-U both in degree and in mode of stacking. In contrast, the existence of different types of stacking interactions in mpU-m62A and U-m62A is suggested in order to explain the NMR and CD data. It is concluded that dinucleoside bisphosphates serve better as a model for the behaviour of trinucleotides than dinucleoside monophosphates. The trinucleotide U-m62A-U adopts a regular single-stranded stacked RNA structure with preference for N-type ribose and gamma+ and beta t backbone torsion angles. The difference in behaviour between the U-m62A- part of U-m62A-U and the dimer U-m62A is seen as a typical example of conformational transmission.

Thermodynamics of stacking and of self-association of the dinucleoside monophosphate m2(6)A-U from proton NMR chemical shifts: differential concentration temperature profile method.

Chemical shifts of base and sugar protons of the modified ribodinucleoside monophosphate N6-dimethyladenylyl(3'-5')uridine (m2(6)A-U) were measured at 100, 360 and 400 MHz in aqueous solution. Seven different samples were used with concentrations ranging from 0.28 mM to 32.7 mM. The temperature was varied from -5 degrees C to 105 degrees C. An internal temperature calibration was used. The effects of intermolecular self-association and of intramolecular stacking on the chemical shifts were quantitatively separated by means of a new approach: differential concentration/temperature profiles (DCTP). Several computational models were tested and the analysis allowed deeper insight into the behaviour of m2(6)A-U at the molecular level. The simple two-state approach for both self-association and stacking already afforded a significant improvement over models in which the association is entirely neglected. A computer least-squares analysis of the chemical shift behaviour of each individual proton yielded thermodynamic parameters for self-association and stacking. However, the two-state model did not suffice to reproduce accurately all of the observations. A satisfactory fit required two additional assumptions: (a) the aromatic protons experience different association shifts in stacked and in unstacked molecules: (b) a temperature-dependent conformational equilibrium exists between sets of unstacked microstates. The stacked state is taken to represent a single conformational species. The implementation of this extended model in the least-squares optimization allowed the reproduction of over one thousand chemical shift observations within experimental error. Thermodynamic equilibrium parameters deduced for intramolecular stacking are: delta H degrees x = -28.8 kJ mol-1, delta S degrees x = -93 J mol-1 K-1. These numbers agree well with those obtained earlier by us from circular dichroism spectra. The equilibrium enthalpy and entropy values deduced for the association process are: delta H degrees A = -35 kJ mol-1 and delta S degrees A = -95 J mol-1 K-1.

Conformational analysis of a modified ribotetranucleoside triphosphate: m6(2)A-U-m6(2)A-U studied in aqueous solution by nuclear magnetic resonance at 500 MHz.

The complete and unequivocal assignment of the 24 ribose proton signals of m6(2)A(1)-U(2)-m6(2)(3)-U(4) by means of 500 MHz NMR spectroscopy at 17 degrees C is given. this assignment is based on scrupulous decoupling experiments carries out at various temperatures. Analysis of the observed chemical shifts and coupling constants of the tetramer shows that the two fragments -m6(2)A(3)-U(4) comprising the 3'-end occur mainly in the classical right-handed stack conformation, whereas the 5'-end the -U(2)- residue appears bulged out in favour of a less well-defined stacking interaction between the bases m6(2)A(1)-and -m6(2)A(3)-. Conformational populations about each of the torsional degrees of freedom along the backbone are discussed. A modernized version of pseudorotation analysis is used to delineate the conformational behaviour of the four ribose rings.