Calculations of Isoelectronic Series of He Using Noninteger n‐Slater Type Orbitals in Single and Double Zeta Approximations

Using integer and noninteger n-Slater type orbitals in single- and double-zeta approximations, the Hartree-Fock-Roothaan calculations were performed for the ground states of first ten cationic members of the isoelectronic series of He atom. All the noninteger parameters and orbital exponents were fully optimized. In the case of noninteger n-Slater type orbitals in double zeta basis sets, the results of calculations obtained are more close to the numerical Hatree-Fock values and the average deviations of our ground state energies do not exceed 2×10^－6 hartrees of their numerical results.     

Use of monolithic supports in proteomics technology

An overview on the utilization of monoliths in proteomics technology will be given. Both silica- and polymer-based monoliths have broad use for microseparation of tryptic peptides in reversed-phase (RP) mode before identification by mass spectrometry (MS) or by MS/MS. For two-dimensional (2D) LC separation of peptides before MS or MS/MS analysis, a combination of ion-exchange, usually cation-exchange (CEX) chromatography with RP chromatography on monolithic supports can be employed. Immobilized metal ion affinity chromatography monoliths with immobilized Fe3+-ions are used for the isolation of phosphopeptides. Monoliths with immobilized affinity ligands are usually applied to the rapid separation of proteins and peptides. Miniaturized reactors with immobilized proteolytic enzymes are utilized for rapid on- or offline digestion of isolated proteins or protein mixtures prior to identification by LC-MS/MS. Monoliths also have broad potential for application in sample preparation, prior to further proteomic analyses. Monolithic supports with large pore sizes can be exploited for the isolation of nanoparticles, such as cells, organelles, viruses and protein aggregates. The potential for further adoption of monolithic supports in protein separation and enrichment of low abundance proteins prior to proteolytic digestion and final LC-MS/MS protein identification will be discussed.     

Effect of nonproximate atomic substitution on excited state intramolecular proton transfer

The central C atom of the OCCCO skeleton of the malonaldehyde molecule is replaced by N, and the effects upon the intramolecular H-bond and the proton transfer are monitored by ab initio calculations in the ground and excited electronic states. The H-bond is weakened in the singlet and triplet states arising from n→π* excitation in both molecules, which is accompanied by a heightened barrier to proton transfer.³ππ* behaves in the same manner, but the singlet ππ* state has a stronger H-bond and lower barrier. Replacement of the central C atom by N strengthens the intramolecular H-bond. Although the proton transfer barrier in the ground state of formimidol is lower than in malonaldehyde, the barriers in all four excited states are higher in the N-analog. The latter substitution also dampens the effect of the n→π* excitation upon the H-bond and increases the excitation energies of the various states, particularly ππ*. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 129–138, 1998     

Proteomic characterization of plasma‐derived clotting factor VIII–von Willebrand factor concentrates

Proteomic methods were used to identify the levels of impurities in three commercial plasma‐derived clotting factor VIII‐von Willebrand factor (FVIII/VWF) concentrates. In all three concentrates, significant amounts of other plasma proteins were found. In Octanate and Haemoctin, two concentrates developed in the 1990s, the major impurities identified were inter‐α inhibitor proteins, fibrinogen and fibronectin. These two concentrates were also found to contain additional components such as clotting factor II (prothrombin) that are known activators of FVIII. In Wilate, a recently developed FVIII/VWF concentrate, the amount of these impurities was significantly reduced. Batch‐to‐batch variations and differences between three investigated products were detected using iTRAQ, an isotope labeling technique for comparative MS, demonstrating the potential value of this technique for quality control analysis. The importance of thorough proteomic investigations of therapeutic FVIII/VWF preparations from human plasma is also discussed.     

Multifunctional polymeric nanoparticles from diverse bioactive agents

We present a rational approach for assembling diverse bioactive agents, such as DNA, proteins, and drug molecules, into core-shell multifunctional polymeric nanoparticles (PNPs) that can be internalized in human breast cancer cells. Using ring-opening metathesis polymerization (ROMP), block copolymers containing small-molecule drug segments (>50% w/w) and tosylated hexaethylene glycol segments were prepared and assembled into PNPs that allowed for the surface conjugation of single-stranded DNA sequences and/or tumor-targeting antibodies. The resulting antibody-functionalized particles were readily uptaken by breast cancer cells that overexpressed the corresponding antigens.     

The magnetic part of the Weyl tensor,and the expansion of discrete universes

We examine the effect that the magnetic part of the Weyl tensor has on the large-scale expansion of space. This is done within the context of a class of cosmological models that contain regularly arranged discrete masses, rather than a continuous perfect fluid. The natural set of geodesic curves that one should use to consider the cosmological expansion of these models requires the existence of a non-zero magnetic part of the Weyl tensor. We include this object in the evolution equations of these models by performing a Taylor series expansion about a hypersurface where it initially vanishes. At the same cosmological time, measured as a fraction of the age of the universe, we find that the influence of the magnetic part of the Weyl tensor increases as the number of masses in the universe is increased. We also find that the influence of the magnetic part of the Weyl tensor increases with time, relative to the leading-order electric part, so that its contribution to the scale of the universe can reach values of \(\sim \)1%, before the Taylor series approximation starts to break down.     

Cosmological solutions with charged black holes

We consider the problem of constructing cosmological solutions of the Einstein–Maxwell equations that contain multiple charged black holes. By considering the field equations as a set of constraint and evolution equations, we construct exact initial data for N charged black holes on a hypersphere. This corresponds to the maximum of expansion of a cosmological solution, and provides sufficient information for a unique evolution. We then consider the specific example of a universe that contains eight charged black holes, and show that the existence of non-zero electric charge reduces the scale of the cosmological region of the space. These solutions generalize the Majumdar–Papapetrou solutions away from the extremal limit of charged black holes, and provide what we believe to be some of the first relativistic calculations of the effects of electric charge on cosmological backreaction.     

In vitro post-stenotic flow quantification and validation using echo particle image velocimetry (Echo PIV)

Echo particle image velocimetry (Echo PIV) presents itself as an attractive in vivo flow quantification technique to traditional approaches. Promising results have been acquired; however, limited quantification and validation is available for post-stenotic flows. We focus here on the comprehensive evaluation of in vitro downstream stenotic flow quantified by Echo PIV and validated in relation to digital particle image velocimetry (DPIV). A Newtonian blood analog was circulated through a closed flow loop and quantified immediately downstream of a 50 % axisymmetric blockage at two Reynolds numbers (Re) using time-averaged Echo PIV and DPIV. Centerline velocities were in good agreement at all Re; however, Echo PIV measurements presented with elevated standard deviation (SD) at all measurements points. SD was improved using increased line density (LD); however, frame rate or field of view (FOV) is compromised. Radial velocity profiles showed close agreement with DPIV with the largest disparity in the shear layer and near-wall recirculation. Downstream recirculation zones were resolved by Echo PIV at both Re; however, magnitude and spatial coverage was reduced compared to DPIV that coincided with reduced contrast agent penetration beyond the shear layer. Our findings support the use of increased LD at a cost to FOV and highlight reduced microbubble penetration beyond the shear layer. High local SD at near-wall measurements suggests that further refinement is required before proceeding to in vivo quantification studies of wall shear stress in complex flow environments.