Dipolar recoupling NMR of biomolecular self-assemblies: determining inter- and intrastrand distances in fibrilized Alzheimer's beta-amyloid peptide

We demonstrate a new method for investigating the structure of self-associating biopolymers using dipolar recoupling NMR techniques. This approach was applied to the study of fibrillar beta-amyloid (Abeta) peptides (the primary component of the plaques of Alzheimer's disease) containing only a single isotopic spin label (13C), by employing the DRAWS (dipolar recoupling with a windowless sequence) technique to measure 13C-13C distances. The 'single-label' approach simplified analysis of DRAWS data, since only interstrand contacts are present, without the possibility of any intrastrand contacts. As previously reported [T.L.S. Benzinger, D.M. Gregory, T.S. Burkoth, H. Miller-Auer, D.G. Lynn, R.E. Botto, S.C. Meredith, Proc. Natl. Acad. Sci. 95 (1998) 13407.], contacts of approximately 5 A were observed at all residues studied, consistent with an extended parallel beta-sheet structure with each amino acid in exact register. Here, we propose that our strategy is completely generalizable, and provides a new approach for characterizing any iterative, self-associating biopolymer. Towards the end of generalizing and refining our approach, in this paper we evaluate several issues raised by our previous analyses. First, we consider the effects of double-quantum (DQ) transverse relaxation processes. Next, we discuss the effects of various multiple-spin geometries on modeling of DRAWS data. Several practical issues are also discussed: these include (1) the use of DQ filtering experiments, either to corroborate DRAWS data, or as a rapid screening assessment of the proper placement of isotopic spin labels; and (2) the comparison of solid samples prepared by either lyophilization or freezing. Finally, data obtained from the use of single labels is compared with that obtained in doubly 13C-labeled model compounds of known crystal structure. It is shown that such data are obtainable in far more complex peptide molecules. These data,taken together, refine the DRAWS method, and demonstrate its precision and utility in obtaining high resolution structural data in complex biomolecular aggregates such as Abeta.     

Synthesis, Structure and Growth Mechanism of ZnS Nanowires with High Aspect Ratio

ZnS nanowires were successfully synthesized through the direct reaction of Zn and S vapor via carbon-assisted chemical evaporation deposition method with Au catalyst. The investigations indicated that the size of ZnS nanowires with a diameter of approximately 40 nm was uniform along the axis of the wire and the surfaces were slick. The ZnS nanowire with a hexagonal wurtzite structure was a typical single crystalline structure. HRTEM and SEAD results demonstrated that the nanowire grew along [100] direction, which was different from the common direction reported in literatures. The growth of nanowires was controlled by vapor-liquid-solid (VLS) mechanism.     

On the nonlinear matrix equation

Based on fixed point theorems for monotone and mixed monotone operators in a normal cone, we prove that the nonlinear matrix equation always has a unique positive definite solution. A conjecture which is proposed in [X.G. Liu, H. Gao, On the positive definite solutions of the matrix equation X^s±A^TX^-tA=I_n, Linear Algebra Appl. 368 (2003) 83–97] is solved. Multi-step stationary iterative method is proposed to compute the unique positive definite solution. Numerical examples show that this iterative method is feasible and effective.     

High-quality hydrogen from the catalyzed decomposition of formic acid by Pd-Au/C and Pd-Ag/C

Pd-Au/C and Pd-Ag/C were found to have a unique characteristic of evolving high-quality hydrogen dramatically and steadily from the catalyzed decomposition of liquid formic acid at convenient temperature, and further this was improved by the addition of CeO(2)(H(2)O)(x).     

Highly enantioselective Michael addition of malononitrile to alpha,beta-unsaturated ketones

The highly enantioselective Michael addition of malononitrile to acyclic and cyclic alpha,beta-unsaturated ketones has been developed. The Michael reaction catalyzed by a primary amine derived from quinidine proceeded smoothly and provided the desired adducts with excellent enantioselectivities (83-97% ee).     

Effect of ancillary ligands on the electronic structures, DNA-binding and spectral properties of [Co(L)2(pip)] (L = phen, bpy, en, tap)

Studies on the electronic structures and related properties of a series of Co(Ш) complexes have been carried out, using the density functional theory (DFT) at the B3LYP/LanL2DZ level. The effect of the ancillary ligands on their electronic structures, DNA-binding affinities and spectra was revealed. The results show that an ancillary ligand has quite important effect on electronic structures and DNA-binding properties of these Co(Ш) complexes. The ancillary ligand possessing a great conjugated structure can effectively improve the DNA-binding affinity of the complex. Meanwhile, introducing a stronger electronegative N atom on the skeleton of ancillary ligand can obviously reduce the LUMO energy of the complex. Based on these findings, a designed complex 4 can be expected to have the greatest K_b value in complexes 1–4. So it may be able to control the interaction between the complex and DNA-base-pairs via varying ancillary ligands. In addition, the electronic absorption spectra of these complexes were calculated and simulated in aqueous solution using the time-dependent DFT (TDDFT) method and the effect of the ancillary ligands on the spectra was also explored. The calculated absorption spectra of these complexes in aqueous solution are in a satisfying agreement with the experimental results, and the properties of experimental absorption bands were theoretically explained in detail.     

Formation of cubane-like photodimers from 2-naphthalenecarbonitrile

Irradiation of 2-naphthalenecarbonitrile (2-NpCN) in solution with a light lambda > 280 nm results in the formation of three rigid cubane-like photodimers, anti-head-to-head 1, anti-head-to-tail 2, and syn-head-to-tail 3, which are not in line with the previously recognized regioselectivity. These cubane-like photodimers have been well characterized by spectroscopic investigation and/or X-ray crystal structural analysis in this work. Moreover, the separation of the optically pure enantiomers of 1, 2, and 3 has been achieved by HPLC resolution.