Computational assessment of environmental hazards of nitroaromatic compounds: influence of the type and position of aromatic ring substituents on toxicity

Structural Chemistry - This study summarizes the results of our recent QSAR and QSPR investigations on prediction of numerous aspects of environmental behavior of nitro compounds. In this study, we...     

ansa-Rare-earth-metal catalysts for rapid and stereoselective polymerization of renewable methylene methylbutyrolactones

Two ansa-half-sandwich rare-earth-metal (REM) dialkyl complexes supported by an ethylene-bridged fluorenyl (Flu)-N-heterocyclic carbene (NHC) ligand, [M{C(2)H(4)(η(5)-Flu-κ(1)-NHC)}(CH(2)SiMe(3))(2)] (M=Y, 1; Lu, 2), and a chiral ansa-sandwich samarocene incorporating a C(2) ligand, [Sm(η(5)-C(12)H(8))(2)(thf)(2)] (3), have been investigated for the coordination-addition polymerization of renewable methylene butyrolactones, α-methylene-γ-butyrolactone (MBL) and γ-methyl-α-methylene-γ-butyrolactone ((γ)MMBL). Both ansa-half-sandwich complexes 1 and 2 exhibit exceptional activity for the polymerization of (γ)MMBL at room temperature in dimethylformamide (DMF); with a 0.25 mol% catalyst loading, quantitative monomer conversion can be achieved under 1 min, giving a high turn-over frequency (TOF) of 24,000 h(-1). This TOF value represents a rate enhancement, by a factor of 8, 22, or 2400, over the polymerizations by unbridged samarocene [Sm(Cp*)(2)(thf)(2)] (Cp*=η(5) -pentamethylcyclopentadienyl), by bridged ansa-samarocene 3 with C(2) ligation, or by the corresponding REM trialkyls without the ansa-Flu-NHC ligation, respectively. Complexes 1 and 2 are also highly active for the polymerization of β-methyl-α-methylene-γ-butyrolactone ((β)MMBL), realizing the first example of the metal-mediated coordination polymerization of this monomer and its copolymerization with (γ)MMBL. More remarkably, the resulting P(β)MMBL homopolymer is highly stereoregular (91% mm) and exhibits a high T(g) of 290 °C. In sharp contrast, catalysts 1 and 2 have poor activity and efficiency in the polymerization of the parent MBL or the acyclic analog methyl methacrylate. Polymerization and kinetic studies using the most active catalyst (1) of the series have uncovered characteristics of its (γ)MMBL polymerization and yielded a unimolecular propagation mechanism. A surprising chain-initiation pathway for the polymerization in DMF by 1 has been revealed, and catalytic polymerization in the presence of an organoacid has also been examined.     

Robust multilayer thin films containing cationic thiol-functionalized gold nanorods for tunable plasmonic properties

Gold nanorods have great potential in a variety of applications because of their unique physical properties. In this article, we present the layer-by-layer (LbL) assembly of thin films containing positively charged gold nanorods that are covalently functionalized by cationic thiol molecules. The cationic gold nanorods are uniformly distributed in ultrathin nanocomposite LbL thin films. We studied the collective surface plasmon resonance coupling in the LbL films via UV-visible spectroscopy and evaluated their application in the surface-enhanced Raman scattering detection of rhodamine 6G probe molecules. Furthermore, we successfully manufactured freestanding nanoscale thin films containing multilayers of gold nanorods with a total thickness of less than 50 nm. The surface morphology and their optical and mechanical properties were systematically investigated, and the polycationic gold nanorods were found to play an important role in manipulating the properties of the nanocomposite thin films. Our findings reveal that such nanorods are excellent building blocks for constructing functional LbL films with tunable plasmonic behavior and robust mechanical properties.     

An efficient basis set representation for calculating electrons in molecules

ABSTRACT

The method of McCurdy, Baertschy, and Rescigno, J. Phys. B, 37, R137 (2004) [1 C.W. McCurdy, M. Baertschy, and T.N. Rescigno, J. Phys. B 37, R137 (2004).[Crossref], [Web of Science ®] , [Google Scholar]] is generalised to obtain a straightforward, surprisingly accurate, and scalable numerical representation for calculating the electronic wave functions of molecules. It uses a basis set of product sinc functions arrayed on a Cartesian grid, and yields 1 kcal/mol precision for valence transition energies with a grid resolution of approximately 0.1 bohr. The Coulomb matrix elements are replaced with matrix elements obtained from the kinetic energy operator. A resolution-of-the-identity approximation renders the primitive one- and two-electron matrix elements diagonal; in other words, the Coulomb operator is local with respect to the grid indices. The calculation of contracted two-electron matrix elements among orbitals requires only O(Nlog?(N)) multiplication operations, not O(N⁴), where N is the number of basis functions; N = n³ on cubic grids. The representation not only is numerically expedient, but also produces energies and properties superior to those calculated variationally. Absolute energies, absorption cross sections, transition energies, and ionisation potentials are reported for 1- (He⁺, H⁺₂), 2- (H₂, He), 10- (CH₄), and 56-electron (C₈H₈) systems.     

Compression behavior of NiO in a diamond cell

Abstract

The compressibility of synthetic polycrystalline NiO was studied in a diamond anvil cell at room temperature utilizing two different X-ray sources. A standard film with a conventional X-ray source and the energy dispersive X-ray diffraction (EDXRD) method with synchrotron radiation were used for data acquisition. In the film method, the sample was compressed in a 4:1 methanol to ethanol solution up to 7 GPa with ruby fluorescence as a pressure calibrant. In the energy dispersive method, NiO powder was mixed with gold and compressed in two different conditions: gasketed and ungasketed up to 30 GPa. In the gasketed run, water was used as the pressure transmitting medium while gold was used as pressure calibrant in both runs.

Hydrostatic compression of NiO in both diffraction methods yields a bulk modulus (K _o) of 187 ± 7 GPa assuming K′ = 4. The compression of gasketed NiO of the synchrotron experiment, however, showed an obvious break at pressure exceeding 4 GPa due to the loss of hydrostaticity. NiO in a nonhydrostatic condition behaves with less compressibility than the hydrostatic results with a nominal K _o of 238 ± 10 GPa. The lower compressibility of NiO in synchrotron runs is attributed to the uniaxial loading effect which was more easily detected by the EDXRD geometry. The discrepancy in the bulk modulus can be attributed to the contrast in the shear strength between the sample and pressure medium and the Poisson effect of the sample under uniaxial loading.     

From approximate balls to approximate ellipses

A ball spans a set of n points when none of the points lie outside it. In Zarrabi-Zadeh and Chan (Proceedings of the 18th Canadian conference on computational geometry (CCCG’06), pp 139–142, 2006) proposed an algorithm to compute an approximate spanning ball in the streaming model of computation, and showed that the radius of the approximate ball is within 3/2 of the minimum. Spurred by this, in this paper we consider the 2-dimensional extension of this result: computation of spanning ellipses. The ball algorithm is simple to the point of being trivial, but the extension of the algorithm to ellipses is non-trivial. Surprisingly, the area of the approximate ellipse computed by this approach is not within a constant factor of the minimum and we provide an elegant proof of this. We have implemented this algorithm, and experiments with a variety of inputs, except for a very pathological one, show that it can nevertheless serve as a good heuristic for computing an approximate ellipse.     

Operational matrix approach for solution of integro-differential equations arising in theory of anomalous relaxation processes in vicinity of singular point

In this paper we study the numerical solution of singular Abel–Volterra integro-differential equations, which are typical for the theory of anomalous diffusion and viscoelastic delayed stresses. The proposed method is based on application of the operational and almost operational matrices to derivatives and integrals in a vicinity of the kernel’s singular point. As examples, two orthonormal systems are considered: Bernstein polynomials and Legendre wavelets. The methods convert the singular integro-differential equation in to a system of algebraic equations that implies two advantages: (i) one does not need to introduce artificial smoothing factors into the singular integrand and (ii) the direct estimation of computational error around singular point is possible via the obtained explicit expression. The examples of numerical solution and their discussion are presented.     

Variance minimization for constrained discounted continuous-time MDPs with exponentially distributed stopping times

This paper deals with minimization of the variances of the total discounted costs for constrained Continuous-Time Markov Decision Processes (CTMDPs). The costs consist of cumulative costs incurred between jumps and instant costs incurred at jump epochs. We interpret discounting as an exponentially distributed stopping time. According to existing theory, for the expected total discounted costs optimal policies exist in the forms of randomized stationary and switching stationary policies. While the former is typically unique, the latter forms a finite set whose number of elements grows exponentially with the number of constraints. This paper investigates the problem when the process stops immediately after the first jump. For costs up to the first jump we provide an index for selection of actions by switching stationary policies and show that the indexed switching policy achieves a smaller variance than the randomized stationary policy. For problems without instant costs, the indexed switching policy achieves the minimum variance of costs up to the first jump among all the equivalent switching policies.