Extraction of Cupric Ions with Ionic Liquids Containing Polypyridine‐type Small Molecules or Peripherally Pyridine‐modified Dendrimers

The hydrophobic ionic liquid N‐butyl‐N‐methylpyrrolidinium bis((trifluoromethyl)sulfonyl)amide (BMP‐TFSA IL), which contains a series of flexible ionophores of polypyridine‐type small molecules or two rigid ionophores of peripherally pyridine‐modified PAMAM dendrimers, was used to extract cupric ions from aqueous solutions. The polypyridine‐type ionophores show good selectivity toward cupric ions at pH 2. The selectivity is affected by the spacing between the two amino groups. However, the pyridine‐modified dendrimers showed poor selectivity, although their extraction efficiency still depended on the pH of the aqueous solution. The ionic liquids that contained small molecular ionophores and their dendrimer analogs were reused after acid washing or electrochemical reduction. During acid washing, the nitrogen atoms of the ionophores were protonated to release the cupric ions into the aqueous phase, and the copper atoms were deposited onto the electrode surface during the electrochemical reduction accompanied by the regeneration of the ionophores.     

Structural stability–chromatographic retention relationship on exenatide diastereomer separation

In this study, the relationship of the structural stability of peptide diastereomers in elution solvents and their retention behaviors in reversed-phase chromatography (RPC) was examined to provide guidance on the solvent selection for a better separation of peptide diastereomers. We investigated the chromatographic retention behaviors of exenatide, a peptide drug for the treatment of type II diabetes mellitus and its three diastereomers using RPC and implicit molecular dynamics (MD) simulation analysis. Three diastereomers involved in the single serine residue mutation of d-form at the 11th, 32nd, and 39th residues were investigated in this study. Results show that the order of the solution structural stability of exenatide and its diastereomers is consistent with their retention order by 36?% acetonitrile/water elution. The sample loading solvent also affects the retention behaviors of exenatide peptide diastereomers in RPC column. Furthermore, a larger solution conformation energy difference of the critical pair of exenatide and its diastereomer (d-Ser39) at the elution solvent of 32?% tetrahydrofuran/water were obtained by MD simulation, and baseline separation was proved experimentally. In summary, we demonstrated that the solution structural stability–chromatographic retention relationship could be a powerful tool for elution solvent selection in peptide chromatographic purification, especially valuable for the separation of critical pair of diastereomers.

Immobilization of large, aliovalent cations in the small-pore zeolite K-natrolite by means of pressure

High-pressure ion exchange of small-pore zeolite K-natrolite allows immobilization of nominally non-exchangeable aliovalent cations such as trivalent europium. A sample exchanged at 3.0(1) GPa and 250 °C contains about 4.7 Eu(III) ions per unit cell, which is equivalent to over 90 % of the K(+) cations being exchanged.     

Synthesis of sulfur-sulfur bond formation from thioamides promoted by 2,3-dichloro-5,6-dicyanobenzoquinone

A mild and efficient synthesis of sulfur-sulfur bond formation from thioformanilides with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) is described. Functionality on the aromatic ring plays a key role in the formation of a sulfur-sulfur bond.     

Global stability analysis for stochastic coupled reaction–diffusion systems on networks

Coupled systems on networks (CSNs) can be used to model many real systems, such as food webs, ecosystems, metabolic pathways, the Internet, World Wide Web, social networks, and global economic markets. This paper is devoted to investigation of the stability problem for some stochastic coupled reaction–diffusion systems on networks (SCRDSNs). A systematic method for constructing global Lyapunov function for these SCRDSNs is provided by using graph theory. The stochastic stability, asymptotically stochastic stability and globally asymptotically stochastic stability of the systems are investigated. The derived results are less conservative than the results recently presented in Luo and Zhang [Q. Luo, Y. Zhang, Almost sure exponential stability of stochastic reaction diffusion systems. Non-linear Analysis: Theory, Methods & Applications 71(12) (2009) e487–e493]. In fact, the system discussed in Q. Luo and Y. Zhang [Q. Luo, Y. Zhang, Almost sure exponential stability of stochastic reaction diffusion systems. Non-linear Analysis: Theory, Methods & Applications 71(12) (2009) e487–e493] is a special case of ours. Moreover, our novel stability principles have a close relation to the topological property of the networks. Our new method which constructs a relation between the stability criteria of a CSN and some topology property of the network, can help analyzing the stability of the complex networks by using the Lyapunov functional method.     

Detecting Higgs bosons with muons at hadron colliders

We investigate the prospects for the discovery of neutral Higgs bosons with a pair of muons by direct searches at the CERN large hadron collider (LHC) as well as by indirect searches in the rare decay Bs→μ⁺μ⁻$B_s\to {\mu }^{+}{\mu }^{-}$ at the Fermilab Tevatron and the LHC. Promising results are found for the minimal supersymmetric standard model, the minimal supergravity (mSUGRA) model, and supergravity models with non-universal Higgs masses (NUHM SUGRA). For tanβ?50$\tan \beta ?50$, we find that (i) the contours for a branching fraction of B(Bs→μ⁺μ⁻)=1×¹⁰⁻⁸$B(B_s\to {\mu }^{+}{\mu }^{-})=1\times {10}^{\mathrm{-8}}$ in the parameter space are very close to the 5σ   contours for pp→b?⁰→bμ⁺μ⁻+X$pp\to b{?}^0\to b{\mu }^{+}{\mu }^{-}+X$, ?⁰=h⁰${?}^0=h^0$, H⁰$H^0$, A⁰$A^0$ at the LHC with an integrated luminosity (L) of 30 fb⁻¹, (ii) the regions covered by B(Bs→μ⁺μ⁻)?5×¹⁰⁻⁹$B(B_s\to {\mu }^{+}{\mu }^{-})?5\times {10}^{\mathrm{-9}}$ and the discovery region for b?⁰→bμ⁺μ⁻$b{?}^0\to b{\mu }^{+}{\mu }^{-}$ with 300 fb⁻¹ are complementary in the mSUGRA parameter space, (iii) in NUHM SUGRA models, a discovery of B(Bs→μ⁺μ⁻)?5×¹⁰⁻⁹$B(B_s\to {\mu }^{+}{\mu }^{-})?5\times {10}^{\mathrm{-9}}$ at the LHC will cover regions of the parameter space beyond the direct search for b?⁰→bμ⁺μ⁻$b{?}^0\to b{\mu }^{+}{\mu }^{-}$ with L=300 fb⁻¹$L=300{\text{fb}}^{\mathrm{-1}}$.     

Induced random fields in the LiHoxY1-xF4 quantum Ising magnet in a transverse magnetic field

The LiHoxY1-xF4 magnetic material in a transverse magnetic field Bx x perpendicular to the Ising spin direction has long been used to study tunable quantum phase transitions in a random disordered system. We show that the Bx-induced magnetization along the x direction, combined with the local random dilution-induced destruction of crystalline symmetries, generates, via the predominant dipolar interactions between Ho3+ ions, random fields along the Ising z direction. This identifies LiHoxY1-xF4 in Bx as a new random field Ising system. The random fields explain the rapid decrease of the critical temperature in the diluted ferromagnetic regime and the smearing of the nonlinear susceptibility at the spin-glass transition with increasing Bx and render the Bx-induced quantum criticality in LiHoxY1-xF4 likely inaccessible.     

Dissociation of heme from gaseous myoglobin ions studied by infrared multiphoton dissociation spectroscopy and Fourier-transform ion cyclotron resonance mass spectrometry

Detachment of heme prosthetic groups from gaseous myoglobin ions has been studied by collision-induced dissociation and infrared multiphoton dissociation in combination with Fourier-transform ion cyclotron resonance mass spectrometry. Multiply charged holomyoglobin ions (hMbn+) were generated by electrospray ionization and transferred to an ion cyclotron resonance cell, where the ions of interest were isolated and fragmented by either collision with Ar atoms or irradiation with 3 mum photons, producing apomyoglobin ions (aMbn+). Both charged heme loss (with [Fe(III)-heme]+ and aMb(n-1)+ as the products) and neutral heme loss (with [Fe(II)-heme] and aMbn+ as the products) were detected concurrently for hMbn+ produced from a myoglobin solution pretreated with reducing reagents. By reference to Ea = 0.9 eV determined by blackbody infrared radiative dissociation for charged heme loss of ferric hMbn+, an activation energy of 1.1 eV was deduced for neutral heme loss of ferrous hMbn+ with n = 9 and 10.     

Augmented coupling interface method for solving eigenvalue problems with sign-changed coefficients

In this paper, we propose an augmented coupling interface method on a Cartesian grid for solving eigenvalue problems with sign-changed coefficients. The underlying idea of the method is the correct local construction near the interface which incorporates the jump conditions. The method, which is very easy to implement, is based on finite difference discretization. The main ingredients of the proposed method comprise (i) an adaptive-order strategy of using interpolating polynomials of different orders on different sides of interfaces, which avoids the singularity of the local linear system and enables us to handle complex interfaces; (ii) when the interface condition involves the eigenvalue, the original problem is reduced to a quadratic eigenvalue problem by introducing an auxiliary variable and an interfacial operator on the interface; (iii) the auxiliary variable is discretized uniformly on the interface, the rest of variables are discretized on an underlying rectangular grid, and a proper interpolation between these two grids are designed to reduce the number of stencil points. Several examples are tested to show the robustness and accuracy of the schemes.