Novel route to styrene/p‐aminostyrene copolymers

A novel route to styrene/p‐aminostyrene copolymers is described that involves the introduction of amino functionality into the structure of pure monodisperse polystyrene. The simple two‐step synthesis involves the introduction of a bromo group into the aromatic ring by electrophilic substitution and then a palladium‐catalyzed reaction with LiN(SiMe₃)₂ followed by an acid and base treatment to release the free amine. All reactions are carried out at room temperature. This approach avoids the difficulties often associated with the preparation of copolymers from incompatible monomers. The technique also gives a product with a precisely known molecular weight and polydispersity, important parameters governing many physical properties. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1282–1286, 2007     

Combined 17O NMR and 11B-31P double resonance NMR studies of sodium borophosphate glasses

17O enriched sodium borophosphate glasses were prepared from isotopically enriched NaPO3 and H3BO3. These glasses have been studied by 17O, 11B and 31P NMR including 17O and 11B multiple quantum magic angle sample spinning (MQMAS), 11B-31P heteronuclear correlation (HETCOR) NMR and 11B{31P} rotational echo double resonance (REDOR). For comparison, the crystalline borophosphates BPO4 and Na5B2P3O13 were included in the investigations. The latter compound shows three sharp 31P resonances at -0.2, -2 and -8 ppm and two BO4 sites that can only be resolved by MQMAS. The 17O NMR spectra were recorded using both the static echo method at medium magnetic field (9.4 T) as well as MAS and MQMAS methods at high field (17.6 T). In total, five oxygen sites were identified in these borophosphate glasses: P-O-P, Na...O-P, P-O-B, B-O-B, Na...O-B. However, these five sites are not present simultaneously in any of the glasses. The 17O MQMAS spectra prove that P-O-B links play a major role in borophosphate glasses. These results are confirmed by the complementary 11B MAS spectra that show the presence of asymmetric and symmetric trigonal groups BO3a and BO3s and two tetrahedral BO4 units. 11B{31P} REDOR NMR is used to give independent information to assign the 11B lines to structural units present in the glasses. These REDOR measurements reveal that B-O-P bonds are present for each borate unit, including the BO3 groups. Particularly, a structural proposal for the two different BO4 resonances is given in terms of a different number of bonded phosphate tetrahedra. The 31P MAS spectra are usually broad and not well resolved. It is shown by 11B-31P HETCOR NMR that a possible structural assignment of a 31P signal at about -20 ppm to Q2 units as in binary sodium phosphate glasses is wrong and that the phosphate tetrahedron belonging to this resonance must be connected to borate groups.     

Quantum-chemical study of the potential anti-cancer drug Ru–NAMI-A in complex with estrogen and the simulated VA and VCD spectra of estrogen, the Ru–NAMI-A drug, and possible/proposed estrogen–Ru–NAMI-A complexes

Following up on an earlier theoretical report by Knapp-Mohammady (Phys Lett A 372:1881–1884, 2008) on the ground state of the neutral Ru complex NAMI-A (trans-imidazoledimethylsulfoxide-tetrachlororuthenate), we first report here a quantum-chemical study of the effect of both oxidation and reduction of the parent molecule to form the anionic and cationic species. The new structures are compared with the equilibrium nuclear structure reported earlier for the neutral complex. We anticipate that one such Ru cluster, with potential as an anti-cancer drug, will interact via an appropriate receptor, rather than directly with DNA. A receptor for NAMI-A binding in here proposed to be the steroid hormone, estrogen, C₁₈H₂₄O₂. The biomolecular structure of the dicomplex is predicted from restricted Hartree–Fock theory and density functional theory (DFT) calculations. The vibrational frequencies of NAMI-A and the dicomplex with estrogen are also reported. Some maps of the ground-state electron-density for the three neutral biomolecular species are finally presented. The use of vibrational spectroscopy, vibrational absorption (VA) and vibrational circular dichorism (VCD) are advocated to be measured, simulated and be used to understand the nature of the interaction of the Ru complex NAMI-A in complex with estrogen. Our aim in presenting these spectral simulations is to motivate the measurement of the VA and VCD spectra of estrogen, the Ru complex NAMI-A and finally of the estrogen–Ru NAMI-A complex. It should also be instructive to measure the VA and VCD spectra of estrogen and the estrogen receptor, both alone, together and finally together in the presence of the Ru NAMI-A complex to substantiate our claim that the Ru complex NAMI-A ties up estrogen, and hence prevents estrogen binding to the estrogen receptor.     

On Estimating the Asymptotic Variance of Stationary Point Processes

We investigate a class of kernel estimators $\widehat{\sigma}^2_n$ of the asymptotic variance σ ² of a d-dimensional stationary point process $\Psi = \sum_{i\ge 1}\delta_{X_i}$ which can be observed in a cubic sampling window $W_n = [-n,n]^d\,$ . σ ² is defined by the asymptotic relation $Var(\Psi(W_n)) \sim \sigma^2 \,(2n)^d$ (as n →? ∞) and its existence is guaranteed whenever the corresponding reduced covariance measure $\gamma^{(2)}_{red}(\cdot)$ has finite total variation. Depending on the rate of decay (polynomially or exponentially) of the total variation of $\gamma^{(2)}_{red}(\cdot)$ outside of an expanding ball centered at the origin, we determine optimal bandwidths b _n (up to a constant) minimizing the mean squared error of $\widehat{\sigma}^2_n$ . The case when $\gamma^{(2)}_{red}(\cdot)$ has bounded support is of particular interest. Further we suggest an isotropised estimator $\widetilde{\sigma}^2_n$ suitable for motion-invariant point processes and compare its properties with $\widehat{\sigma}^2_n$ . Our theoretical results are illustrated and supported by a simulation study which compares the (relative) mean squared errors of $\widehat{\sigma}^2_n$ for planar Poisson, Poisson cluster, and hard-core point processes and for various values of n b _n .     

New Potential Biocatalysts by Laccase Immobilization in PVA Cryogel Type Carrier

Laccases are enzymes belonging to the Oxidoreductases class. These enzymes may be good biocatalysts for different processes, at laboratory and industrial levels. A successful use at industrial scale demands a higher stability of the enzyme. As an easy way to obtain longer life biocatalysts, the immobilization process is recommended. Thus, the paper presents different ways of obtaining new biocatalysts by a laccase covalent immobilization on a macroporous carrier based on poly(vinyl alcohol) cryogel. Different procedures of covalent immobilization are described, the newly obtained biocatalysts being characterized. According to the experimental data, the stability of the immobilized enzyme increased and the pH profile changed, compared with those of the free enzyme.     

The CH–π Interaction in Protein–Carbohydrate Binding: Bioinformatics and In Vitro Quantification

The molecular recognition of carbohydrates by proteins plays a key role in many biological processes including immune response, pathogen entry into a cell, and cell–cell adhesion (e.g., in cancer metastasis). Carbohydrates interact with proteins mainly through hydrogen bonding, metal-ion-mediated interaction, and non-polar dispersion interactions. The role of dispersion-driven CH–π interactions (stacking) in protein–carbohydrate recognition has been underestimated for a long time considering the polar interactions to be the main forces for saccharide interactions. However, over the last few years it turns out that non-polar interactions are equally important. In this study, we analyzed the CH–π interactions employing bioinformatics (data mining, structural analysis), several experimental (isothermal titration calorimetry (ITC), X-ray crystallography), and computational techniques. The Protein Data Bank (PDB) has been used as a source of structural data. The PDB contains over 12 000 protein complexes with carbohydrates. Stacking interactions are very frequently present in such complexes (about 39 % of identified structures). The calculations and the ITC measurement results suggest that the CH–π stacking contribution to the overall binding energy ranges from 4 up to 8 kcal mol⁻¹. All the results show that the stacking CH–π interactions in protein–carbohydrate complexes can be considered to be a driving force of the binding in such complexes.     

Uncoupling evolutionary groundwater‐surface water flows using the Crank–Nicolson Leapfrog method

Consider an incompressible fluid in a region Ω_f flowing both ways across an interface into a porous media domain Ω_p saturated with the same fluid. The physical processes in each domain have been well studied and are described by the Stokes equations in the fluid region and the Darcy equations in the porous media region. Taking the interfacial conditions into account produces a system with an exactly skew symmetric coupling. Spatial discretization by finite element method and time discretization by Crank–Nicolson LeapFrog give a second‐order partitioned method requiring only one Stokes and one Darcy subphysics and subdomain solver per time step for the fully evolutionary Stokes‐Darcy problem. Analysis of this method leads to a time step condition sufficient for stability and convergence. Numerical tests verify predicted rates of convergence; however, stability tests reveal the problem of growth of numerical noise in unstable modes in some cases. In such instances, the addition of time filters adds stability. © 2012 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2013     

Four dimensional regular algebras with point scheme,anonsingular quadric in P3

In [22], a class of four-dimensional, quadratic, Artin-Schelter regular algebras was introduced, whose point scheme is the graph of an automorphism of a nonsingular quadric in P³. These algebras are the first examples of quadratic Artin-Schelter regular algebras whose defining relations are not determined by the point scheme and, hence, not determined by the algebraic data obtained from the point modules. In this paper, we study these algebras via their line modules. In particular, the set of lines in P³ that correspond to left line modules is not the set of lines in P³ that correspond to right line modules. Our analysis focuses on a distinguished member R _λ of this class of algebras, where R _λ is a twist by a twisting system of the other algebras. We prove that R _λ is a finite module over its center and that its central Proj is a smooth quadric inP⁴.