Hierarchical assembly of two-dimensional homochiral nanocavity arrays

We demonstrate the rational design of nanoporous two-dimensional supramolecular structures by the hierarchical assembly of organic molecules and transition metal atoms at surfaces. Single-molecule level observations with scanning tunneling microscopy monitor the successive aufbau of structures with increasing complexity. From the primary components secondary mononuclear chiral complexes are formed, which represent antecedents for tertiary polynuclear metal-organic nanogrids. These nanogrids represent the constituents of the eventually evolving two-dimensional networks comprising homochiral nanocavity arrays. Our findings visualize the evolution of complex matter in an exemplary way: from per se achiral species via chiral intermediates to mesoscale dissymmetric structures.     

cis-Dihydroxylation and epoxidation of alkenes by [Mn(2)O(RCO(2))(2)(tmtacn)(2)]: tailoring the selectivity of a highly H(2)O(2)-efficient catalyst

The carboxylic acid promoted cis-dihydroxylation and epoxidation of alkenes catalyzed by [MnIV2O3(tmtacn)2]2+ 1 employing H2O2 as oxidant is described. The use of carboxylic acids at cocatalytic levels not only is effective in suppressing the inherent catalase activity of 1, but also enables the tuning of the catalyst's selectivity. Spectroscopic studies and X-ray analysis confirm that the control arises from the in situ formation of carboxylate-bridged dinuclear complexes, for example, 2 {[MnIII2O(CCl3CO2)2(tmtacn)2]2+} and 3 {[MnII2(OH)(CCl3CO2)2(tmtacn)2]+}, during catalysis. For the first time, the possibility to tune, through the carboxylate ligands employed, both the selectivity and activity of dinuclear Mn-based catalysts is demonstrated. To our knowledge, the system 1/2,6-dichlorobenzoic acid (up to 2000 turnover numbers for cis-cyclooctanediol) is the most active Os-free cis-dihydroxylation catalyst reported to date.     

Interplay of magnetic and superconducting proximity effects in ferromagnet-superconductor-ferromagnet trilayers

We present theoretical results on the interplay of magnetic and superconducting orders in diffusive ferromagnet-superconductor-ferromagnet trilayers. The induced triplet superconducting correlations throughout the trilayer lead to an induced spin magnetization. We include self-consistency of the order parameter in the superconducting layer at arbitrary temperatures, arbitrary interface transparency, and any relative orientation of the exchange fields in the two ferromagnets. We propose to use the torque on the trilayer in an external magnetic field as a probe of the presence of triplet correlations in the superconducting phase.     

Optic axis determination accuracy for fiber-based polarization-sensitive optical coherence tomography

We present a generalized analysis of fiber-based polarization-sensitive optical coherence tomography with an emphasis on determination of sample optic axis orientation. The polarization properties of a fiber-based system can cause an overall rotation in a Poincaré sphere representation such that the plane of possible measured sample optic axes for linear birefringence and diattenuation no longer lies in the QU-plane. The optic axis orientation can be recovered as an angle on this rotated plane, subject to an offset and overall indeterminacy in sign such that only the magnitude, but not the direction, of a change in orientation can be determined. We discuss the accuracy of optic axis determination due to a fundamental limit on the accuracy with which a polarization state can be determined as a function of signal-to-noise ratio.     

Solubility of CO2, CO, and H2 in the ionic liquid [bmim][PF6] from Monte Carlo simulations

This work reports predictions from molecular simulation results for the solubility of the single gases carbon dioxide, carbon monoxide, and hydrogen in the ionic liquid 1-N-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF6]) at temperatures from 293 to 393 K and at pressures up to 9 MPa. The predictions are achieved by Gibbs ensemble Monte Carlo simulations at constant pressure and temperature (NpT-GEMC). The intermolecular forces are approximated by effective pair potentials for the pure gases and by a quantum-chemistry-based pair potential for [bmim][PF6]. The interactions between unlike groups are described using common mixing rules without any adjustable binary interaction parameter. The simulation results for the solubility of hydrogen agree within their statistical uncertainty with experimental data, whereas the results for carbon monoxide and carbon dioxide reveal somewhat larger deviations.     

Evidence for neuroprotective properties of human umbilical cord blood cells after neuronal hypoxia <Emphasis Type="Italic">in vitro</Emphasis>

Background  

One of the most promising options for treatment of stroke using adult stem cells are human umbilical cord blood (HUCB) cells that were already approved for therapeutic efficacy in vivo. However, complexity of animal models has thus far limited the understanding of beneficial cellular mechanisms. To address the influence of HUCB cells on neuronal tissue after stroke we established and employed a human in vitro model of neuronal hypoxia using fully differentiated vulnerable SH-SY5Y cells. These cells were incubated under an oxygen-reduced atmosphere (O₂< 1%) for 48 hours. Subsequently, HUCB mononuclear cells (MNC) were added to post-hypoxic neuronal cultures. These cultures were characterized regarding to the development of apoptosis and necrosis over three days. Based on this we investigated the therapeutic influence of HUCB MNC on the progression of apoptotic cell death. The impact of HUCB cells and hypoxia on secretion of neuroprotective and inflammatory cytokines, chemokines and expression of adhesion molecules was proved.     

Configuration Space of Surface–Surface Contact

We consider a space X of constant curvature (Euclidean, elliptic, and hyperbolic space, and the sphere). The set of isometries of X transforming a surface such that it touches a second surface is called the configuration space of surface–surface contact. We investigate when this subset of Isom(X) is an immersed submanifold (which depends on the principal curvatures of the surfaces involved), and when it is an embedded submanifold (which depends on the size and shape of the given surfaces).     

Polyamide resin: A novel immunoadsorbent

A solid phase assay for radiolabeled antibody synthesizedde novo in vitro has been described (1). The solid phase consists of antigen covalently bound to bromacetyl cellulose, a useful but difficult to prepare immunoadsorbent. Herein, we describe the preparation of polyamide resin immunoadsorbent and the procedure for coupling antigen to the polymer. Data are presented that show that polyamide resin-Ag? conjugates can replace bromacetyl cellulose-Ag conjugates. The usefulness of this easily prepared and inexpensive immunoadsorbent is discussed.