H2S·HOH or H2O·HSH, which is more stable in the water-hydrogen sulfide complex?

High-level ab initio calculations are carried out to study the relative stability of the two hydrogen bonded structures of water-hydrogen sulfide complex, one with water as the proton donor (A) and the other with hydrogen sulfide as the proton donor (B). The results show that structure A is considerably more stable than B at the correlated level, which is in contrast with previous results obtained from Hartree-Fock calculations.     

Solution bundle for a class of impulsive differential inclusions on Banach spaces

In this paper a class of impulsive differential inclusions is investigated. The existence of solution bundle is proved. And we also construct a nonlinear semigroup of operators on cb(E) (closed-bounded subset of E) to describe the set of attainable states.     

Stability and Hopf bifurcation analysis on a simplified BAM neural network with delays

A delay-differential equation modelling a bidirectional associative memory (BAM) neural network with three neurons is investigated. Its dynamics are studied in terms of local analysis and Hopf bifurcation analysis. By analyzing the associated characteristic equation, its linear stability is investigated and Hopf bifurcations are demonstrated. The stability and direction of the Hopf bifurcation are determined by applying the normal form theory and the center manifold reduction. Numerical simulation results are given to support the theoretical predictions.     

Nonlinear rheological behavior of silica filled solution‐polymerized styrene butadiene rubber

The reinforcement and nonlinear viscoelastic behavior have been investigated for silica (SiO₂) filled solution‐polymerized styrene butadiene rubber (SSBR). Experimental results reveal that the nonlinear viscoelastic behavior of the filled rubber is similar to that of unfilled SSBR, which is inconsistent with the general concept that this characteristic comes from the breakdown and reformation of the filler network. It is interesting that the curves of either dynamic storage modulus (G′) or loss tangent (tan δ) versus strain amplitude (γ) for the filled rubber can be superposed, respectively, on those for the unfilled one, suggesting that the primary mechanism for the Payne effect is mainly involved in the nature of the entanglement network in rubbery matrix. It is believed there exists a cooperation between the breakdown and reformation of the filler network and the molecular disentanglement, resulting in enhancing the Payne effect and improving the mechanical hysteresis at high strain amplitudes. Moreover, the vertical and the horizontal shift factors for constructing the master curves could be well understood on the basis of the reinforcement factor f(φ) and the strain amplification factor A(φ), respectively. The surface modification of SiO₂ causes a decrease in f(φ), which is ascribed to weakeness of the filler–filler interaction and improvement of the filler dispersion. However, the surface nature of SiO₂ hardly affects A(φ). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2594‐2602, 2007     

[Co(amp)2Cl2]2[ZnCl4]体系中两对称异构体的2D NMR研究

The two symmetrical isomers in [Co(amp)₂Cl₂]₂[ZnCl₄](amp=2-(Aminomethyl)pyridine) system were syn-thesized by general oxidation method and were separated by chromatography and recrystallization method. Their configurations were assigned by using 2D NMR techniques, particularly the NOESY NMR spectra. Solvent used was Me₂SO-d₆ with the central peak of the CD₃ septet as the reference ( ₁₃C,δ 39.37; ₁H,δ 2.49 relative to SiMe₄). Cation exchange media used was Dowex 50Wx 2(H⁺ form, 200～400mesh; Biorad).     

Multifunctional peptide-assembled micelles for simultaneously reducing amyloid-β and reactive oxygen species

The excessive production and deposition of amyloid-β (Aβ) is one of the most important etiologies of Alzheimer''s disease (AD). The interaction between Aβ and metal ions produces aberrant reactive oxygen species (ROS), which induce oxidative stress and accelerate the progression of AD. To reduce Aβ plaques and ROS to maintain their homeostasis is an emerging and ingenious strategy for effective treatment of AD. Herein, we report the rational design of multifunctional micelles (MPGLT) based on a polymer-grafted peptide to simultaneously clear Aβ and ROS for AD therapy. The MPGLT integrating three functional peptides as a ROS scavenger (tk-GSH), β-sheet breaker (LP) and an autophagy activator (TK) respectively, could capture and degrade Aβ. Meanwhile, the tk-GSH on the surface of MPGLT effectively scavenges the intracellular ROS. Consequently, MPGLT reduced the cytotoxicity of Aβ and ROS. In vivo animal studies using an AD mouse model further showed that MPGLT could transport across the blood–brain barrier for decreasing the Aβ plaque and eliminating ROS in vivo. This peptide micelle-based synergistic strategy may provide novel insight for AD therapy.

Multifunctional micelles based on a peptide–polymer for simultaneously targeting Aβ degradation and ROS scavenging for AD therapy.     

Asymmetric Negishi reaction for sterically hindered couplings: synthesis of chiral binaphthalenes

A new synthetic approach affording, for the first time chiral binaphthalene derivatives via an asymmetric Negishi reaction, in good yields (55–95%) and good enantioselectivities (49–85% ee), is reported.     

Increasing the enantioselectivity of cyclopentanone monooxygenase (CPMO): profile of new CPMO mutants

A series of cyclohexanones substituted at the 4-position with a selection of hydrophobic and hydrophilic groups were used as substrates in the evaluation of six new cyclopentanone monooxygenase (CPMO) mutants. These mutants were obtained through evolutionary modifications in two specific regions of the CPMO’s putative active site. Several mutant enzymes with improved enantioselectivity were identified. Analysis of the results, in terms of a diamond model, illustrates how a family of cyclohexanone substrates may be used to explore putative active sites of Baeyer–Villiger monooxygenases (BVMOs) and to design productive mutations for specific substrates.     

Conformation and size of humic substances: Effects of major cation concentration and type,pH, salinity,and residence time

The macromolecular structure of humic substances (HS), i.e. molecular size, shape, conformation, and weight is believed to control key physico-chemical reactions in aquatic systems. However, these properties of HS are still deeply a matter of debate. Furthermore, they are affected by solution physico-chemical parameters such as ionic strength, pH, and chemical composition, etc. To better understand aggregation processes of HS in natural waters, the effects of cation concentration and type, water composition, and pH on the size and conformation of the Suwannee River Humic Acid (SRHA) were investigated with synthetic solutions. The size and the conformation of the SRHA in NaCl and CaCl₂ solutions at different concentrations (0.001–0.5 M) and pH (4.5–9.3) were determined using the photon correlation spectroscopy (PCS) and transmission electron microscopy (TEM), respectively. In addition, dissolved organic matter (DOM) samples collected from the Adour estuary along a salinity gradient were imaged by TEM. The average size of the SRHA measured by PCS increased with pH and ionic strength. This behavior was confirmed by TEM micrographs. The increase in pH and CaCl₂ engendered aggregation of the SRHA. Two aggregation steps were identified, a big increase in HS size occurred for small changes in CaCl₂ concentrations in the range <0.02 M CaCl₂, and a slight increase occured for higher concentrations in the range >0.02 M CaCl₂. The parallel analysis of SRHA by PCS and TEM allowed overcoming the limits for both techniques.Comparable results were found for the DOM samples from the Adour estuary (South West of France). The conformation and size of the HS network of these samples varied with the salinity gradient. TEM images demonstrated that, HS have a branched open network in freshwater whereas they have a more compacted and close network with increasing salinity.