Nickel-catalyzed cycloaddition of alkynes and isocyanates

A mild and general route for preparing 2-pyridones from isocyanates and diynes is described. Ni imidazolyidene complexes were used to mediate cyclizations between both internal and terminal diynes with aryl and alkyl isocyanates. In addition, the efficacy of this protocol allows for the preparation of a fused seven-membered pyridone and for three component cyclizations.     

An energy approach to the link-up of multiple cracks in thin aluminum alloy sheets

An energy approach has been used in the study of the coalescence or linkage of multiple cracks in aluminum alloy sheets. The study was motivated by concern for the structural integrity of aging aircraft. Forty reported tests for 2024-T3 aluminum panels with a major crack and several multiple-site damage (MSD) cracks have been analyzed via a simple computational model with a Dugdale–Barenblatt [D.S. Dugdale, J. Mech. Phys. Solids 8 (1960) 100–104; G.I. Barenblatt, in: H.L. Dryden, Th. VonKarman (Eds.), Advances in Applied Mechanics, vol. II, 1962, pp. 55–130] type of plastic or inelastic deformation. For simplicity, the computational model considers only the plastic interaction between the major crack and two symmetrically adjacent MSD cracks in an infinite sheet under remote tensile stress. By following the approach given in [B. Cotterell, J. K. Reddel, Int. J. Fract. 13 (1977) 267–277], the specific work to cause ligament failure is found to be a linear function of the normal extent of the confined plastic region for most tests considered. A few exceptions to this linear relation are attributed to the limitation of the employed computational model. A new criterion and an engineering method to predict crack link-up in an MSD sheet are proposed based on this specific work concept, and they have been demonstrated through application to stiffened panels.     

A model study on the mechanism and kinetics for the dissociation of water anion

Quantum chemical computations using both density functional theory (B3LYP functional) and wavefunction (MP2 and CCSD(T)) methods, with the 6-311++G(3df,2p) and aug-cc-pVnZ (n = D,T,Q) basis sets, in conjunction with a polarizable continuum model (PCM) method for treating structures in solution, were carried out to look again at a series of small negatively charged water species [(H₂O)_n]^•–. For each size n of [(H₂O)_n]^•– in aqueous solution with n = 2, 3, and 4, two distinct structural motifs can be identified: a classical water radical anion formed by hydrogen bonds and a molecular pincer in which the excess electron is directly interacting with H atoms. In aqueous solution, both motifs have comparable energy content and likely coexist and compete for the ground state. Some water anion isomers can dissociate when interaction with a water molecule, [(H₂O)_n]^•– + H₂O → H^•(H₂O)_m + OH^–(H₂O)_n–m, through successive hydrogen transfers with moderate energy barriers. This reaction can also be regarded as a water-splitting process in which the H transfers involved take place mainly within a water trimer, whereas other water molecules tend to stabilize transition structures through microsolvation rather than direct participation. Calculated absolute rate constants for the reversed reaction H^•(H₂O)₂ + OH^–(H₂O)₂ → [(H₂O)₄]^•־ + H₂O with both H and D isotopes agree well with the experimentally evaluated counterpart and lend a kinetic support for the involvement of a tetramer unit.     

Elucidating the binding mechanism of thione-containing mercaptopurine and thioguanine drugs to small gold clusters

Density functional theory methods were employed to clarify the adsorption/desorption behaviors of the thione-containing mercaptopurine and thioguanine drugs on the gold surface using both small Au₆ and Au₈ clusters as model reactants. Structural features, thermodynamic parameters, bonding characteristics, and electronic properties of the resulting complexes were investigated using the Perdew–Burke–Ernzerhof (PBE) and LC-BLYP functionals along with correlation-consistent basis sets, namely cc-pVDZ-PP for gold and cc-pVTZ for non-metals. Computed results show that the drug molecules tend to anchor on the gold cluster at the S atom with binding energies around −34 to −40 kcal/mol (in vacuum) and − 28 to −32 kcal/mol (in aqueous solution). As compared to Au₈, Au₆ undergoes a shorter recovery time and a larger change of energy gap that could be converted to an electrical signal for selective detection of the drugs. Furthermore, interactions between the drugs and gold clusters are reversible processes and a drug release mechanism was also proposed. Accordingly, the drugs are able to separate from the gold surface due to either a slight change of pH in tumor cells or the presence of cysteine residues in protein matrices.     

Determination of the 15N chemical shift anisotropy in natural abundance samples by proton-detected 3D solid-state NMR under ultrafast MAS of 70 kHz

Chemical shift anisotropy (CSA) is a sensitive probe of electronic environment at a nucleus, and thus, it offers deeper insights into detailed structural and dynamic properties of different systems, for example, chemical, biological, and materials. Over the years, massive efforts have been made to develop recoupling methods that reintroduce CSA interaction under magic angle spinning (MAS) conditions. Most of them require slow or moderate MAS (≤20 kHz) and isotopically enriched samples. On the other hand, to the best of the authors' knowledge, no ¹³C or ¹⁵N CSA recoupling schemes at ultrafast MAS (≥60 kHz) suitable for cost-effective natural abundant samples have been developed. We present here a proton-detected 3D ¹⁵N CS/¹⁵N CSA/¹H CS correlation experiment which employs ¹H indirect detection for sensitivity enhancement and a γ-encoded -symmetry-based CSA recoupling scheme. In particular, two different symmetries, that is, R8³₇ and R10⁴₉, are first tested, in a 2D ¹⁵N CSA/¹H CS version, on [U-¹⁵N]-L-histidine·HCl·H₂O as a model sample under 70 kHz MAS. Then the 3D experiment is applied on glycyl-L-alanine at natural abundance, resulting in site-resolved ¹⁵N CSA lineshapes from which CSA parameters are retrieved by SIMPSON numerical fittings. We demonstrate that this 3D R-symmetry-based pulse sequence is highly robust with respect to wide-range offset mismatches and weakly dependent to rf inhomogeneity within mis-sets of ±10% from the theoretical value.     

A New Sesquiterpene Glycoside from Leaves of Bombax ceiba

Chemistry of Natural Compounds - A new sesquiterpene glycoside, ceibanoside (1), was isolated from the leaves of Bombax ceiba, together with the previously-reported quercetin (2), kaempferol (3),...     

Second-Order Optimality Conditions for Infinite-Dimensional Quadratic Programs

Journal of Optimization Theory and Applications - Second-order necessary and sufficient optimality conditions for local solutions and locally unique solutions of generalized quadratic programming...     

A new projection method for a class of variational inequalities

In this paper, we revisit the numerical approach to variational inequality problems involving strongly monotone and Lipschitz continuous operators by a variant of projected reflected gradient method. Contrary to what done so far, the resulting algorithm uses a new simple stepsize sequence which is diminishing and nonsummable. This brings the main advantages of the algorithm where the construction of aproximation solutions and the formulation of convergence are done without the prior knowledge of the Lipschitz and strongly monotone constants of cost operators. The assumptions in the formulation of theorem of convergence are also discussed in this paper. Numerical results are reported to illustrate the behavior of the new algorithm and also to compare with others.     

Wavelet bases in the Lebesgue spaces on the field of p-adic numbers

In this paper we prove that p-adic wavelets form an unconditional basis in the space L ^r (? _p ⁿ ) and give the characterization of the space L ^r (? _p ⁿ ) in terms of Fourier coefficients of p-adic wavelets.Moreover, the Greedy bases in the Lebesgue spaces on the field of p-adic numbers are also established.